Inorganic nitrogen dynamics in intertidal rocky biofilms and sediments of the Douro River estuary (Portugal)

In this study rates of oxygen, ammonium (NH₄ ⁺), nitrate (NO₃ ⁻), nitrite (NO₂ ⁻), and nitrous oxide (N₂O) fluxes, nitrogen (N) fixation, nitrification, and denitrification were compared between two intertidal sites for which there is an abundant global literature, muddy and sandy sediments, and two sites representing the rocky intertidal zone where biogeochemical processes have scarcely been investigated. In almost all sites oxygen production rates greatly exceeded oxygen consumption rates. During daylight, NH₄ ⁺ and NO₃ ⁻ uptake rates together with ammonification could supply the different N requirements of the primary producer communities at all four sites; N assimilation by benthic or epilithic primary producers was the major process of dissolved inorganic nitrogen (DIN) removal; N fixation, nitrification, and denitrification were minor processes in the overall light DIN cycle. At night, distinct DIN cycling processes took place in the four environments, denitrification rates ranged from 9 ± 2 to 360 ± 30 μmol N₂ m⁻² h⁻¹, accounting for 10–48% of the water column NO₃ ⁻ uptake; nitrification rates varied from 0 to 1712 ± 666 μmol NH₄ ⁺ m⁻² h⁻¹. A conceptual model of N cycle dynamics showed major differences between intertidal sediment and rocky sites in terms of the mean rates of DIN net fluxes and the processes involved, with rocky biofilm showing generally higher fluxes. Of particular significance, the intertidal rocky biofilms released 10 times the amount of N₂O produced in intertidal sediments (up to 17 ± 6 μmol N₂O m⁻² h⁻¹), representing the highest N₂O release rates ever recorded for marine systems. The biogeochemical contributions of intertidal rocky substrata to estuarine and coastal processes warrant future detailed investigation.     

Nitrogen losses through sediment denitrification in Boston Harbor and Massachusetts Bay

Sediment denitrification is a microbial process that converts dissolved inorganic nitrogen in sediment porewaters to N₂ gas, which is subsequently lost to the atmosphere. In coastal waters, it represents a potentially important loss pathway for fixed nitrogen which might otherwise be available to primary producers. Currently, data are lacking to adequately assess the role of denitrification in reducing or remediating the effects of large anthropogenic nitrogen loads to the coastal zone. This study describes the results of 88 individual measurements of denitrification (as a direct flux of N₂ gas) in sediment cores taken over a 3-yr period (1991–1994) from six stations in Boston Harbor, nine stations in Massachusetts Bay, and two stations in Cape Cod Bay. The dataset is unique in its extensive spatial and temporal coverage and includes the first direct measurements of denitrification for North Atlantic shelf sediments. Results showed that rates of denitrification were significantly higher in Boston Harbor (mean=54, range<5–206 μmol N₂ m^?2 h^?1) than in Massachusetts Bay (mean=23, range<5–64 μmol N₂ m^?2 h^?1). Highest rates occurred in areas with organic-rich sediments in the harbor, with slower rates observed for low-organic sandy sediments in the harbor and at shallow shelf stations in the bay. Lowest rates were found at the deepest shelf stations, located in Stellwagen Basin in Massachusetts Bay. Observed rates were correlated with temperature, sediment carbon content, and benthic macrofaunal activity. Seasonally, highest denitrification rates occurred in the summer in Boston Harbor and in the spring and fall in Massachusetts Bay, coincident with peak phytoplankton blooms in the overlying water column. Despite the fact that sediment denitrification rates were high relative to rates reported for other East Coast estuaries, denitrification losses accounted for only 8% of the annual total nitrogen load to Boston Harbor, a consequence perhaps, of the short water-residence times (2–10 d) of the harbor.     

A Mini-Review of the Contribution of Benthic Microalgae to the Ecology of the Continental Shelf in the South Atlantic Bight

Benthic microalgae (BMA) inhabit the upper few centimeters of shelf sediments. This review summarizes the current information on BMA communities in the South Atlantic Bight (SAB) region of the Southeastern US continental shelf to provide insights into the potential role of these communities in the trophodynamics and biogeochemical cycling in shelf waters. Benthic irradiance is generally 2–6% of surface irradiance in the SAB region, providing sufficient light to support BMA primary production over 80–90% of the shelf width. BMA biomass greatly exceeds that of integrated phytoplankton biomass in the overlying water column on an areal basis. The SAB appears to have lower BMA biomass, but higher production than most temperate continental shelves. Annual production estimates average 101 and 89 g C m^?2 year^?1 for 5–20 and >?20 depth intervals, respectively. However, high variation in rates and biomass in time and space make comparisons between studies difficult. Submarine groundwater discharge (SGD) rather than the water column or in situ N regeneration from organic matter maybe the major “new” N source for BMA. The estimated supply of N (1.2 mmol N m^?2 day^?1) by SGD closely approximates the rates needed to support BMA primary production (3.1 to 1.6 mmol N m^?2 day^?1) in the sediments of the SAB. Identifying the source(s) of fixed N supporting the BMA community is essential for understanding the carbon dynamics and net ecosystem metabolism within the large area (76,000 km²) of the continental shelf in the SAB as well other temperate shelves worldwide.     

Benthic nitrogen cycling traversing the Peruvian oxygen minimum zone

Benthic nitrogen (N) cycling was investigated at six stations along a transect traversing the Peruvian oxygen minimum zone (OMZ) at 11°S. An extensive dataset including porewater concentration profiles and in situ benthic fluxes of nitrate (NO₃⁻), nitrite (NO₂⁻) and ammonium (NH₄⁺) was used to constrain a 1-D reaction-transport model designed to simulate and interpret the measured data at each station. Simulated rates of nitrification, denitrification, anammox and dissimilatory nitrate reduction to ammonium (DNRA) by filamentous large sulfur bacteria (e.g. Beggiatoa and Thioploca) were highly variable throughout the OMZ yet clear trends were discernible. On the shelf and upper slope (80-260 m water depth) where extensive areas of bacterial mats were present, DNRA dominated total N turnover (?2.9 mmol N m⁻² d⁻¹) and accounted for ?65% of NO₃⁻ + NO₂⁻ uptake by the sediments from the bottom water. Nonetheless, these sediments did not represent a major sink for dissolved inorganic nitrogen (DIN = NO₃⁻ + NO₂⁻ + NH₄⁺) since DNRA reduces NO₃⁻ and, potentially NO₂⁻, to NH₄⁺. Consequently, the shelf and upper slope sediments were recycling sites for DIN due to relatively low rates of denitrification and high rates of ammonium release from DNRA and ammonification of organic matter. This finding contrasts with the current opinion that sediments underlying OMZs are a strong sink for DIN. Only at greater water depths (300-1000 m) did the sediments become a net sink for DIN. Here, denitrification was the major process (?2 mmol N m⁻² d⁻¹) and removed 55-73% of NO₃⁻ and NO₂⁻ taken up by the sediments, with DNRA and anammox accounting for the remaining fraction. Anammox was of minor importance on the shelf and upper slope yet contributed up to 62% to total N₂ production at the 1000 m station. The results indicate that the partitioning of oxidized N (NO₃⁻, NO₂⁻) into DNRA or denitrification is a key factor determining the role of marine sediments as DIN sinks or recycling sites. Consequently, high measured benthic uptake rates of oxidized N within OMZs do not necessarily indicate a loss of fixed N from the marine environment.     

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.     

Benthic nutrient fluxes in the intertidal flat within the Changjiang （Yangtze River） Estuary

In an annual cycle from March 2005 to February 2006, benthic nutrient fluxes were measured monthly in the Dongtan intertidal flat within the Changjiang （Yangtze River） Estuary. Except for NH4^＋, there always showed high fluxes from overlying water into sediment for other four nutrients. Sediments in the high and middle marshes, covered with halophyte and consisting of macrofauna, demonstrated more capabilities of assimilating nutrients from overlying water than the low marsh. Sampling seasons and nutrient concentrations in the overlying water could both exert significant effects on these fluxes. Additionally, according to the model provided by previous study, denitrification rates, that utilizing NO3- transported from overlying water （Dw） in Dongtan sediments, were estimated to be from -16 to 193 μmol·h^-1·m^-2 with an average value of 63 μmol·h^-1·m^-2 （n=18）. These estimated values are still underestimates of the in-situ rates owing to the lack of consideration of DN, i.e., denitrification supported by the local NO3^- production via nitrification.     

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.     

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.     

Nitrogen cycling and ecosystem exchanges in a Virginia tidal freshwater marsh

Tidal freshwater marshes are diverse habitats that differ both within and between marshes in terms of plant community composition, sediment type, marsh elevation, and nutrient status. Because our knowledge of the nitrogen (N) biogeochemistry of tidal freshwater systems is limited, it is difficult to assess how these marshes will respond to long-term progressive nutrient loading due to watershed development and urbanization. We present a process-based mass balance model of N cycling in Sweet Hall marsh, a pristine (i.e., low nutrient)Peltandra virginica-Pontederia cordata dominated tidal freshwater marsh in the York River estuary, Virginia. The model, which was based on a combination of field and literature data, revealed that N cycling in the system was largely conservative. The mineralization of organic N to NH₄ ⁺ provided almost twice as much inorganic N as was needed to support marsh macrophyte and benthic microalgal primary production. Efficient utilization of porewater NH₄ ⁺ by nitrifiers and other microbes resulted in low rates of tidal NH₄ ⁺ export from the marsh and little accumulation of NH₄ ⁺ in marsh porewaters. Inputs of N from the estuary and atmosphere were not critical in supporting marsh primary production, and served to balance N losses due to denitrification and burial. A comparison of these results with the literature suggests that the relative importance of tidal freshwater marsh N cycling processes, including plant productivity, organic matter mineralization, microbial immobilization, and coupled nitrification-denitrification, are largely independent of small changes in water column N loading. Although very high (millimolar) concentrations of dissolved inorganic N can affect processes including denitrification and plant productivity, the factors that cause the switch from efficient N recycling to a more open N cycle have not yet been identified.     

Nitrogen dynamics in nontidal littoral sediments: Role of microphytobenthos and denitrification

Previous measurements from cool microtidal temperate areas suggest that microphytobenthic incorporation of nitrogen (N) exceeds N removal by denitrification in illuminated shallow-water sediments. The present study investigates if this is true also for fully nontidal sediments in the Baltic Sea., Sediment-water fluxes of inorganic (DIN) and, organic nitrogen (DON) and oxygen, as well as denitrification, were measured in early autumn and spring, in light and dark, at four sites representing different sediment types. All sediments were autotrophic during the daytime both in the autumn and spring. On a 24-h time scale, they were autotrophic in the spring and heterotrophic in early autumn. Sediments funcitoned as sources of DIN and DON during the autumn and sinks during the spring, with DON fluxes dominating or being as important as DIN fluxes. Microphytobenthos (MPB) activity controlled fluxes of both DIN and DON. Significant differences between sites were found, although sediment type (sand or silt) had no consistent effect on the magnitude of MPB production or nutrient fluxes. The clearest effect related to sediment type was found for denitrification, although only in the autumn, with higher rates in silty sediments. Estimated N assimilation by MPB, based on both net primary production (0.7–6.5 mmol N m⁻² d⁻¹) and on 80% of gross primary production (1.9–9.4 mmol N m⁻² d⁻¹) far exceeded measured rates of denitrification (0.01–0.16 mmol N m⁻² d⁻¹). A theoretical calculation showed that MPB may incorporate between 40% and 100% of the remineralized N, while denitrification removes, <5%. MPB assimilation of N appears to be a far more important N consuming process than denitrification in these nontidal, shallow-water sediments.     

Grain size and geochemistry of surface sediments in northwestern continental shelf of the South China Sea

Eighty-six surface sediments collected from the northwestern continental shelf of the South China Sea (SCS) were analyzed for grain size distribution, calcium carbonate, organic carbon, and major and trace element compositions to investigate sediment provenance and factors controlling their geochemical composition. Sediments from the eastern continental shelf of Hainan Island have higher sand and lower clay content, while the samples from the nearshore Hainan Island have higher contents of gravel and clay. Calcium carbonate contents in samples show a positive correlation with water depth in northwestern shelf of SCS, suggesting that it is related to biological factors. However, the nearshore sediments have higher contents of organic carbon compared to those of the outer shelf, possibly suggesting that the terrigenous organic matter usually deposited in nearshore environments such as bays and estuaries. Compared with the upper continental crust, the samples have relatively lower contents of SiO₂ and Al₂O₃, higher than those of the Pearl and Red river sediments. The low contents of K₂O and Na₂O in sediments from the northwestern continental shelf are consistent with intense chemical weathering in the river basin due to the seasonally hot and humid climate regime. The sediments mainly consist of three components, including the gravel fraction composed of calcareous debris, the sand fraction composed of quartz, and the silt and clay fractions mainly composed of clay minerals. The content of each component depends on grain size, sediment source, biogenesis, and hydrodynamic conditions, which finally controls the chemical composition of the sediments. The distributions of Co/Al₂O₃, Cr/Al₂O₃, and Zr/Sc ratios for sediments in the northwestern continental shelf suggest that source rocks are mainly composed of felsic rocks rather than mafic rocks. There is a distinct difference in sediment source between eastern and western shelf sediments; the eastern shelf sediments are characterized by high Zr/Sc ratios mainly derived from the Pearl River, while the western shelf sediments have relatively low values of Zr/Sc indicating a main contribution possibly sourced from the Red River Basin. Terrigenous materials from Hainan Island usually influence the geochemistry of sediments deposited in the nearshore area.     

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.     

Role of a strong oxygen-deficient zone in the preservation and degradation of organic matter: a carbon budget for the continental margins of northwest Mexico and Washington State

Rates of organic carbon oxidation in marine sediments were determined for the continental margins of northwest Mexico and Washington State, with the goal of assessing the role of oxygen in the preservation of organic matter on a margin with a strong oxygen-deficient zone and on a typical western continental margin. Total carbon oxidation rates (including rates for individual electron acceptors: O₂, NO₃⁻, and SO₄⁼) were determined at depths ranging from 100 to 3000 m on both margins. Carbon oxidation rates were generally higher on the Washington margin than on the Mexican margin. The relative importance of the different electron acceptors varied across the two margins and was related primarily to the availability of O₂ and NO₃⁻ from the overlying water. The relative contribution of O₂ consumption increased in deeper sediments (>2000 m) as aerobic processes began to dominate the total carbon oxidation rate. Denitrification rates were highest in Washington sediments; however, denitrification represented a larger fraction of the total carbon oxidation rate in the Mexican sediments (∼40% for Mexico vs. ∼30% for Washington). Sulfate reduction accounted for as much as 79% of the total carbon oxidation rate in shallow sediments and less than 20% in deep sediments on both margins. The offshore trends in carbon oxidation rate appeared to be related to the organic carbon input rate. Pore-water O₂ and NO₃⁻ penetration depths were shallowest in nearshore stations and increased offshore. Regeneration ratios of C:N:P reveal “non-Redfield” behavior on both margins. Carbon budgets for the two margins demonstrate that off Mexico, a much greater percentage of the organic matter produced in the surface ocean reached the sediments (>15% vs. <8% for Mexico and Washington, respectively). On the Mexican margin, ∼8% of the primary production escaped oxidation in the surface sediments to be permanently buried, as compared with only ∼1.2% of the primary production on the Washington margin. This suggests that oxygen-deficient conditions on Mexican margin are linked to enhanced carbon preservation.     

Benthic metabolism and nutrient cycling along an estuarine salinity gradient

Benthic metabolism and nutrient exchange across the sediment-water interface were examined over an annual cycle at four sites along a freshwater to marine transect in the Parker River-Plum Island Sound estuary in northeastern Massachusetts, U.S. Sediment organic carbon content was highest at the freshwater site (10.3%) and decreased along the salinity gradient to 0.2% in the sandy sediments at the marine end of the estuary. C:N ratios were highest in the mid estuary (23:1) and lowest near the sea (11:1). Chlorophyll a in the surface sediments was high along the entire length of the estuary (39–57 mg chlorophyll a m⁻²) but especially so in the sandy marine sediments (172 mg chlorophyll a m⁻²). Chlorophyll a to phaeophytin ratios suggested most chlorophyll is detrital, except at the sandy marine site. Porewater sulfide values varied seasonally and between sites, reflecting both changes in sulfate availability as overlying water salinity changed and sediment metabolism. Patterns of sediment redox potential followed those of sulfide. Porewater profiles of inorganic N and P reflected strong seasonal patterns in remineralization, accumulation, and release. Highest porewater NH₄ ⁺ values were found in upper and mid estuarine sediments, occasionally exceeding 1 mM N. Porewater nitrate was frequently absent, except in the sandy marine sediments where concentrations of 8 μM were often observed. Annual average respiration was lowest at the marine site (13 mmol O₂ m⁻² d⁻¹ and 21 mmol TCO₂ m⁻² d⁻¹) and highest in the mid estuary (130 mmol O₂ m⁻² d⁻¹ and 170 mmol TCO₂ m⁻² d⁻¹) where clam densities were also high. N₂O and CH₄ fluxes were low at all stations throughout the year: Over the course, of a year, sediments varied from being sources to sinks of dissolved organic C and N, with the overall spatial pattern related closely to sediment organic content. There was little correlation between PO₄ ³⁻ flux and metabolism, which we attribute to geochemical processes. At the two sites having the lowest salinities, PO₄ ³⁻ flux was directed into the sediments. On average, between 22% and 32% of total system metabolism was attributable to the benthos. The mid estuary site was an exception, as benthic metabolism accounted for 95% of the total, which is attributable to high densities of filter-feeding clams. Benthic remineralization supplied from less than 1% to over 190% of the N requirements and 0% to 21% of the P requirements of primary producers in this system. Estimates of denitrification calculated from stoichiometry of C and N fluxes ranged from 0% for the upper and mid estuary site to 35% for the freshwater site to 100% of sediment organic N remineralization at the marine site. We hypothesize that low values in the upper and mid estuary are attributable to enhanced NH₄ ⁺ fluxes during summer due to desorption of exchangeable ammonium from rising porewater salinity. NH₄ ⁺ desorption during summer may be a mechanism that maintains high rates of pelagic primary production at a time of low inorganic N inputs from the watershed.     

Denitrification in anoxic sediments supported by biological nitrate transport

Biologically available nitrogen (fixed N) is removed from the oceans by metabolic conversion of inorganic N forms (nitrate and ammonium) to N₂ gas. Much of this removal occurs in marine sediments, where reaction rates are thought to be limited by diffusion. We measured the concentration and isotopic composition of major dissolved nitrogen species in anoxic sediments off the coast of California. At depths below the diffusive penetration of nitrate, we found evidence of a large nitrate pool transported into the sediments by motile microorganisms. A ∼20‰ enrichment in ¹⁵N and ¹⁸O of this biologically transported nitrate over bottom water values and elevated [N₂] and δ¹⁵N-N₂ at depth indicate that this nitrate is consumed by enzymatic redox reactions with the production of N₂ as the end product. Elevated N₂O concentrations in pore waters below the nitrate diffusion depth confirm that these reactions include the denitrification pathway. A data-constrained model shows that at least 31% of the total N₂ production in anoxic sediments is linked to nitrate bio-transport. Under suboxic/anoxic regimes, this nitrate bio-transport augments diffusive transport, thus increasing benthic fixed nitrogen losses and the reducing burial efficiency of sedimentary organic matter.     

Copper in surface waters of the Bering Sea

Copper concentrations have been measured in surface <75 m waters of the central Bering Sea. Concentrations of 2–4 nmole kg^?1 were measured in the Zhemchung Canyon region where water depths are greater than 1000 m. Concentrations are higher 2–25 nmole kg^?1 on the shallow <100 m continental shelf, inshore of a hydrographic front at the 100 m isobath. Copper-depth profiles on the continental shelf water mass are dominated by Cu concentrations increasing toward the sediments. These trends may be maintained by a flux of Cu from surficial sediments. A frontal system over the 100 m isobath acts to control the flux of Cu, a significant part of which apparently emanates from the sediments, between the continental shelf and the central Bering Sea basin. The benthic shelf Cu flux was constrained to be less than 3 nmole cm^?2 yr^?1.     

An explosion seismology investigation of the continental margin west of the Hebrides, Scotland, at 58°N

During summer 1975, a line of large shots was fired across the continental margin between the Rockall Trough and the Hebridean shelf along 58°N. Arrivals were observed at temporary seismic stations set up across Scotland and in northwestern Ireland. A clear P₂ phase was observed to cross the margin and a converted phase P₁ also seen on the records is interpreted as travelling in the sub-sedimentary oceanic crust of Rockall Trough and in the upper continental crust beneath the shelf.The continental crust beneath the Hebridean shelf is estimated to be 27 ± 2 km thick, with P_g = 6.22 ± 0.03 km/s and P_n = 8.01 ± 0.04 km/s as determined by time-term analysis. P_g delays on the outer shelf are interpreted in terms of a seaward thickening wedge of Mesozoic sediments which pre-date the split. P_n beneath the Rockall Trough was poorly determined at 8.20 ± 0.17 km/s and the Moho is estimated to be 18 ± 2 km deep at 58°N. This and other seismic and gravity work indicates a northward thickening of the crust along the Rockall Trough, accounting for the northward decrease in the height of the slope.Our results, and those of gravity interpretations, indicate a relatively abrupt transition between continental and oceanic crust, possibly correlating with the lack of major shelf subsidence. This is attributed to a relatively cool origin for this margin. The main thinning of the continental crust beneath the slope is attributed to outslip of continental crustal material into and beneath the newly forming oceanic crust during the first few million years after the split, possibly enhanced by pre-split stretching.     

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.     

Oxygen and nutrient dynamics within mats of the filamentous macroalga Chaetomorpha linum

Concentration profiles of O₂, NH₄ ⁺, NO₃ ⁻, and PO₄ ³⁻ were measured at high spatial resolution in a 12-cm thick benthic mat of the filamentous macroalga Chaetomorpha linum. Oxygen and nutrient concentration profiles varied depending on algal activity and water turbulence. High surface irradiance stimulated O₂ production in the surface layers and introduced O₂ to deeper parts of the mat while the bottom layers of the mat and the underlying sediment were anoxic. Nutrient concentrations were highest in the bottom layers of the mat directly above the sediment nutrient source and decreased towards the surface layers due to algal assimilation and enhanced mixing with the overlying water column. Increased turbulence during windy periods resulted in more homogeneous oxygen and nutrient concentration profiles and shifted the oxic-anoxic interface downward. Denitrification within the mat, as measured by the isotope pairing technique on addition of ¹⁵NO₃ ⁻, was found to take place directly below the oxic-anoxic interface. Denitrification activity was always due to coupled nitrification-denitrification, whereby nitrifiers in the mat utilize NH₄ ⁺ diffusing from below and O₂ diffusing from above. The denitrification rate in the mat ranged from 22 μmol m⁻² h⁻¹ to 28 μmol m⁻² h⁻¹, approximately equivalent to that measured in the surrounding nonvegetated sediment. Although sediment denitrification is suppressed when the sediment surface is covered by a dense macroalgal mat, the denitrification zone may migrate up into the mat. In eutrophic estuaries with a large area of macroalgal cover, the physical structure and growth stage of algal mats may thus play an important role in the regulation of nitrogen removal by denitrification.     

Energy sources for diagenesis: Evidence from the Black Sea

Complex investigations of recent and Drevnechernomorian (ancient Black Sea) sediments from the outer shelf, continental slope, and deep-water basin of the Russian Black Sea sector have been carried out using samples collected during cruise of the R/V Professor Shtokman organized by the Institute of Oceanology of the Russian Academy of Sciences (March 2009) and expedition of “YUZHMORGEO” (summer 2006). Rates of the main anaerobic processes during diagenesis (sulfate reduction, dark CO₂ fixation, methanogenesis, and methane oxidation) were studied for the first time in sediment cores of the studied area. Two peaks in the rate of microbial processes and two sources of these processes were identified: the upper peak near the water-sediment contact is related to the solar energy (OM substrate of the water column) and the lower peak at the base of the Drevnechernomorian sediments with high(>1000 μM) methane concentration related to the energy of anaerobic methane oxidation. The neogenic labile OM formed during this process is utilized by other groups of microorganisms. According to experimental data, the daily rate of anaerobic methane oxidation is many times higher than that of methanogenesis, which unambiguously indicates the migration nature of the main part of methane.