Benthic nutrient remineralization in a coastal lagoon ecosystem

In situ measurements of the exchange of ammonia, nitrate plus nitrite, phosphate, and dissolved organic phosphorus between sediments and the overlying water column were made in a shallow coastal lagoon on the ocean coast of Rhode Island, U.S.A. The release of ammonia from mud sediments in the dark (20–440 μmol per m² per h) averaged ten times higher than from a sandy tidal flat (0–60 μmol per m² per h), and while mud sediments also released nitrate and phosphate, sandy sediments took up these nutrients. Fluxes of nutrients from mud sediments, but not from sandy areas, markedly increased with temperature. Ammonia release rates for mud sediments in the light (0–350 μmol per m² per h) were lower than those in the dark and it is estimated that some 25% of the ammonia released to the water column on an annual basis may be intercepted by the benthic microfloral community. Estimates of the annual net exchange of nutrients across the sediment-water interface, weighted by sediment type for the lagoon as a whole, showed a release of 450 mmol per m² of ammonia, 5 mmol per m² of phosphate, 5 mmol per m² of dissolved organic phosphorus, and an uptake of 80 mmol per m² of nitrate. Although rates of ammonia and nitrate exchange were comparable to those described for the deeper heterotrophic bottom communities of nearby Narragansett Bay, rates of benthic phosphate release were significantly lower. On an annual basis the Bay benthos released approximately 20 times more inorganic phosphate per unit area than did the lagoon benthos. As a result., the N/P ratio for the flux from the sediments was 74∶1 in the lagoon, compared with 16∶1 in “average” marine plankton and 8∶1 for the benthic flux from Narragansett Bay. The lack of remineralized phosphate in the lagoon, is reflected in water, column phosphate concentrations (always <1 μm) and water column N/P ratios (annual N/P=27) and suggests that the lagoon may show phosphate limitation rather than the nitrogen limitation commonly associated with marine systems.     

Biogeochemical cycling in an organic rich coastal marine basin—II. Nutrient sediment-water exchange processes

The release of remineralized N and P from the organic-rich anoxic sediments of Cape Lookout Bight is controlled by processes occurring within the sediment column and at the sediment-water interface. The relatively rapid rates of temperature dependent microbial degradation of organic matter support seasonally varying nutrient fluxes ranging from 20 to 1200 μmol·m^?2·hr^?1 for dissolved ammonium and from ? 20 to 120 μmol·m^?2·hr^?1 for total dissolved phosphate (measured in situ over the period October, 1976 to October, 1978). Molecular diffusion along steep vertical pore water concentration gradients measured simultaneously cannot explain the high fluxes observed during warmer months. Gradients for ammonium and phosphate ranged from 0.33 to 1.10 and from 0 to 0.29 μmol·cm^?3_pw·cm^?1_s respectively. These high summertime fluxes appear to result from increased sediment-water transport associated with bubble tubes created and maintained by low-tide methane gas bubble ebullition. When these tubes are present, apparent bulk sediment diffusivities calculated from concurrent studies of methane and radon-222 sediment-water exchange are 1.0–3.1 times greater than molecular diffusivities. Nutrient fluxes calculated via Fick's first law taking into account this enhanced transport and the differential diffusive mobilities of dissolved ammonium, phosphate and phosphate ion pairs indicate that removal by aerobic adsorption and/or biological uptake at the sediment-water interface plays an important role in controlling nutrient exchange in these sediments.     

Bivalve contribution to benthic metabolism in a California Lagoon

Populations of suspension feeding bivalves constitute a metabolically important component of the benthos in Colorado Lagoon, Long Beach, California. Oxygen and nutrient flux were measuredin situ at monthly intervals over a two-year period. Estimates of bivalve metabolism were based on regressions of oxygen and ammonium flux on a measure of clam biomass adjusted allometrically. The introduced bivalve,Mercenaria mercenaria, occurs at maximum densities exceeding 400 per m². Based on mean densities (143 per m²), bivalves contributed more than 50% of the 77 mg O₂ per m² per hr mean annual oxygen uptake and the 191 μM per m² per hr mean ammonium release. Although bivalve biomass was not correlated with other inorganic nutrient flux, on an annual basis the sediments were a source of phosphate (26 μM per m² per hr annual average, range 5 to 50) and a small sink for nitrate and nitrite. Net primary production, ammonium flux, and phosphate flux showed great annual variability while respiration was relatively constant. Total community oxygen uptake was not correlated with temperature. Long term incubations revealed no obvious rhythms having a period between four hours and four days. The benthic flux of ammonium and phosphate was calculated to supply more than the annual requirement of Lagoon phytoplankton.     

The influence of upwelling and short-term changes in concentrations of nutrients in the water column on fluxes across the surface of a salt marsh

Oceanic upwelling results in the intermittent intrusion of cold ocean water enriched in nitrate, and to a lesser extent soluble reactive phosphorus (SRP), into the Kariega Estuary (South Africa). Laboratory measocosm experiments were conducted to determine the effects of such changes on fluxes of dissolved nutrients across the surface of a salt marsh within the estuary. When replicate mesocosms of the tidal creek and salt marsh were inundated with nonupwelled water (at 25°C and nitrate concentrations of 4.5 μmoll^?1), nitrate fluxes in both regions were small, and the tidal creek exhibited net uptake (negative value) of nitrate from the water column (?85 μmol m^?2 tide^?1), and the marsh, net release (positive values; 113 μmol m^?2 tide^?1). When the mesocosms were inundated with upwelled water, at 16°C and with nitrate concentrations of 24.2 μmol l^?1, both regions exhibited large net uptakes of nitrate (?514 μmol m^?2 tide^?1 and ?226 μmol m^?2 tide^?1 for the tidal creek and salt marsh, respectively). In contrast to nitrate, the fluxes of nitrite, ammonium, and SRP were not significantly different under upwelling and nonupwelling conditions, probably because initial concentrations in the two water types were similar. To determine the extent to which the nitrate uptakes were caused by decreased water temperatures or increased concentrations of nitrate, experiments were conducted in which mesocosms were inundated with water with a range of nitrate concentrations (1.8–25 μmol l^?1), at two temperatures representative of summer upwelling (16°C) and nonupwelling conditions (25°C). In both regions, the net fluxes of nitrate were positively correlated with initial concentrations of nitrate in the water column. For any given concentration, the fluxes at 16°C fell within the range of values at 25°C, indicating that the shifts in fluxes caused by upwelling occurred in response to increased concentrations in the water column and not reduced temperatures.     

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.     

Dynamics of NH4 + and NO3 − uptake in the water column of the Neuse River Estuary,North Carolina

In an attempt to more fully understand the dissolved inorganic nitrogen dynamics of the Neuse River estuary, ¹⁵NH₄ ⁺ and ¹⁵NO₃ ^? uptake rates were measured and daily depth-integrated rates calculated for seven stations distributed along the salinity gradient. Measurements were made at 2–3-wk intervals from March 1985 to February 1989. Significant dark NH₄ ⁺ uptake occurred and varied both spatially and seasonally, accounting for as much as 95% of light uptake with the median being 33%. Apparent NH₄ ⁺ uptake ranged from 0.001 μmol N 1^?1 h^?1 to 4.2 μmol N 1^?1 h^?1, with highest rates occurring during late summer-fall in the oligohaline estuary. Apparent NH₄ ⁺ uptake was significantly related to NH₄ ⁺ concentration (p<0.01); however, the regression explained <3% of the variation. Daily-integrated NH₄ ⁺ uptake ranged from 0.1 mmol N m^?2 d^?1 to 133 mmol N m^?2 d^?1 and followed the trend of apparent uptake. Annual NH₄ ⁺ uptake of the estuary was significantly lower in 1988 than for any other year. Dark uptake of NO₃ ^? was only 14% of maximum light uptake. Apparent NO₃ ^? uptake rates ranged from 0.001 μmol N 1^?1 h^?1 to 1.84 μmol N 1^?1 h^?1 with highest rates occurring in the oligohaline estuary. Apparent NO₃ ^? uptake was significantly related to NO₃ ^? concentration (p<0.01); however, the regression explained <5% of the variation. In general, NO₃ ^? uptake was only 20% of total dissolved inorganic nitrogen (DIN) uptake. Daily-integrated NO₃ ^? uptake ranged from 0.1 mmol N m^?2 d^?1 to 53 mmol N m^?2 d^?1 and followed similar patterns of apparent uptake. Annual NH₄ ⁺ uptake was 11.39 mol N m^?2 yr^?1, 10.28 mol N m^?2 Yr^?1, 10.93 mol N m^?2 yr^?1, and 7.38 mol N m^?2 yr^?1, and 1.84 mol N m^?2 yr^?1, with the 4-yr mean being 10.0. Annual NO₃ ^? uptake was 3.12 mol N m^?2 yr^?1, 3.40 mol N m^?2 yr^?1, 1.96 mol N m^?2 yr^?1, and 1.84 mol N m^?2 yr^?1, with the 4-yr mean being 2.6. The total annual DIN uptake was more than twice published estimates of phytoplankton DIN demand, indicating that there is an important heterotrophic component of DIN uptake occurring in the water column. The extrapolation of nitrogen demand from primary productivity results in serious underestimates of estuarine nitrogen demand for the Neuse River estuary and may be true for other estuaries as well.     

Significance of subtidal sediments to heterotrophically-mediated oxygen and nutrient dynamics in a temperate estuary

Sediment-water exchanges of ammonium (NH₄ ⁺), nitrate + nitrite (NO_x ^?), filterable reactive phosphorus (FRP, primarily ortho-phosphate), and oxygen (O₂) under aphotic (heterotrophic) conditions were determined at 2–5 stations in the Neuse River Estuary, from 1987 to 1989. Shallow (1 m), sandy stations were sampled along the salinity gradient. Fluxes from deep (>2 m) sites were compared to the shallow sites in two salinity zones. Grain size became finer and organic content increased with depth in the oligohaline zone but not in the mesohaline zone. Net release of NH₄ ⁺ and FRP occurred at all sites. Fluxes varied from slight uptake to releases of 200–500 μmol m^?2 h^?1 (NH₄ ⁺) and 150–900 μmol m^?2 h^?1 (FRP). Net NO_x ^? exchange was near zero, but were ±100 μmol m^?2 h^?1 over the year. Release of NH₄ ⁺ and FRP from the shallow sandy stations decreased with distance down the estuary, but O₂ uptake did not change. The deeper oligohaline site had twofold higher rates of NH₄ ⁺ and FRP release and O₂ uptake than the shallow site, but no differences occurred between depths in the mesohaline zone. Temperature and organic content were important controls for all fluxes, but water column NO_x ^? concentration was also important in regulating NO_x ^? exchanges. Ratios of oxygen consumption to NH₄ ⁺ release were near the predicted ratio (Redfield model) at oligohaline sites but increased down estuary at mesohaline sites. This may be due to greater nitrification rates promoted by autotrophy in the sediments.     

Tidal nitrogen exchanges across a freshwater wetland succession gradient in the upper Cooper River,South Carolina

Tidal freshwater sections of the Cooper River Estuary (South Carolina) include extensive wetlands, which were formerly impounded for rice culture during the 1,700s and 1,800s. Most of these former rice fields are now open to tidal exchange and have developed into productive wetlands that vary in bottom topography, tidal hydrography and vegetation dominants. The purpose of this project was to quantify nitrogen (N) transport via tidal exchange between the main estuarine channel and representative wetland types and to relate exchange patterns to the succession of vegetation dominants. We examined N concentration and mass exchange at the main tidal inlets for the three representative wetland types (submerged aquatic vegetation [SAV], floating leaf vegetation, and intertidal emergent marsh) over 18-21 tidal cycles (July 1998–August 2000). Nitrate + nitrite concentrations were significantly lower during ebb flow at all study sites, suggesting potential patterns of uptake by all wetland types. The magnitude of nitrate decline during ebb flow was negatively correlated with oxygen concentration, reflecting the potential importance of denitrification and nitrate reduction within hypoxic wetland waters and sediments. The net tidal exchange of nitrate + nitrite was particularly consistent for the intertidal emergent marsh, where flow-weighted ebb concentrations were usually 18–40% lower than during flood tides. Seasonal patterns for the emergent marsh indicated higher rates of nitrate + nitrite uptake during the spring and summer (> 400 μmol N m^-2 tide^-1) with an annual mean uptake of 248 ± 162 μmol m^–2 tide^–1. The emergent marsh also removed ammonium through most of the year (207 ± 109 μmol m^–2 tide^–1), and exported dissolved organic nitrogen (DON) in the fall (1,690 ± 793 μmol m^–2 tide^–1), suggesting an approximate annual balance between the dissolved inorganic N uptake and DON export. The other wetland types (SAV and floating leaf vegetation) were less consistent in magnitude and direction of N exchange. Since the emergent marsh site had the highest bottom elevation and the highest relative cover of intertidal habitat, these results suggest that the nature of N exchange between the estuarine waters and bordering wetlands is affected by wetland morphometry, tidal hydrography, and corresponding vegetation dominants. With the recent diversion of river discharge, water levels in the upper Cooper estuary have dropped more than 10 cm, leading to a succession of wetland communities from subtidal habitats toward more intertidal habitats. Results of this study suggest that current trends of wetland succession in the upper Cooper River may result in higher rates of system-wide inorganic N removal and DON inputs by the growing distributions of intertidal emergent marshes.     

Nitrogen limitation of phytoplankton in a shallow embayment in northern Puget Sound

The effect of nutrient enrichments on natural phytoplankton assemblages was examined in six experiments conducted from June to October 1992. Short-term (4 d to 7 d) nutrient enrichment bioassays were incubated in situ in Padilla Bay, a slough-fed estuary in northern Puget Sound, Washington. Ammonium additions (15 μM) significantly (p<0.001) stimulated phytoplankton biomass accumulation during all six experiments. In two experiments, nitrate additions (15 μM) significantly stimulated accumulation of phytoplankton biomass during October, but not September. Addition of phosphate (1.0 μM) or silicate (15 μM) alone did not stimulate phytoplankton biomass accumulation during any of the experiments. In most experiments, phytoplankton response was greatest in combination treatments of ammonium and phosphate. Dissolved inorganic nutrient concentrations in the containers decreased during all incubations, but showed the greatest reduction in treatments receiving nitrogen. Dissolved inorganic nitrogen (DIN) to phosphate (PO₄ ^3?) ratios were below 16∶1 during all experiments, suggesting the potential for nitrogen limitation. In three experiments, the response of photosynthetic nanoplankton (<20 μm) to ammonium additions was compared to that of the total phytoplankton assemblages. Accumulation of nanoplankton biomass exceeded that of the total phytoplankton during two experiments in August but showed no significant response to ammonium additions in October. Results from the bioassays, the low DIN∶PO₄ ^3? ratios, and the reduction in nutrient concentrations in the containers provide evidence for potential nitrogen limitation of phytoplankton production during summer in Padilla Bay.     

The effects of in situ light reduction on the growth of two subtropical seagrasses,Thalassia testudinum and Halodule wrightii

The effects of in situ light reductions on two species of subtropical seagrasses, Thalassia testudirum (reduced to 14% and 10% of surface irradiance; SI) and Halodule wrightii (reduced to 16% and 13% SI) were examined over a 10-mo period (October 1992-September 1993) in relation to leaf elongation rates, sediment pore-water ammonium, and blade chlorophyll concentrations. No significant changes in pore-water ammonium levels were noted among treatments with time, but blade chlorophyll concentrations in both species were higher in plants exposed to the darkest treatments (10% and 13% SI) relative to controls exposed to 50% SI. In all treatments, blade chlorophyll concentrations were highest and chlorophyll a:b ratios lowest during the warner months, coincident with higher water temperatures. Leaf elongation rates in T. testudinum plants decreased relative to unshaded controls after 1 mo of treatment in autumn, but no significant differences in leaf elongation were noted among treatments for H. wrightii in late autumn or winter when very low growth rates (<0.1 cm shoot^?1 d^?1) were recorded. There were no differences between treatments during the spring growth period for T. testudinum (no data are available for H. wrightii), suggesting that growth (ca. 1 cm shoot^?1 d^?1) was probably not related to available light but was supported by belowground reserves. After 10 mo of treatment, all H. wrightii plants at 13% SI (1,600 mol m^?2 yr^?1) and 16% SI (2,000 mol m^?2 yr^?1) disappeared from experimental plots; similarly, no T. testudinum plants exposed to 10% SI (1,300 mol m^?2 yr^?1) remained, although 4% of the plants at 14% SI (1,800 mol m^?2 yr^?1) survived nearly 12 mo of reduced irradiance. In neither species were leaf elongation rates, which showed little change among treatments, a reliable indicator of the underwater light environment.     

Ammonium regeneration and biomass of macrozooplankton and ctenophores in Great South Bay,New York

The rate of zooplankton ammonium regeneration was measured in Great South Bay, Long Island, New York, between July 1982 and May 1984. Ammonium excretion by macrozooplankton (>200 μm) ranged from 7 μg atoms NH₄ ¹⁺?N m^?3 d^?1 in winter to 156 μg-atoms NH₄ ¹⁺?N m^?3 d^?1 in spring. Ammonium excretion by ctenophores was greater than or equivalent to that of macrozooplankton during the period of ctenophore biomass maximum in summer and fall. The temperature coefficient (Q₁₀) for NH₄ ¹⁺ excretion was 1.74 from 2.2 to 27.5°C for macrozooplankton and 1.63 between 17 and 26°C for the ctenophores. Ammonium nitrogen excretion by macrozooplankton and ctenophores combined, accounted for 1 to 3% of phytoplankton nitrogen requirements in summer when primary productivity was high and 39% in the spring. *** DIRECT SUPPORT *** A01BY040 00005     

Methane distribution and cycling in Tomales Bay, California

Cycling of methane (CH₄) in Tomales Bay, a 28-km² temperature estuary in northern California with relatively low inputs of organic carbon, was studied over a 1-yr period. Water column CH₄ concentrations showed spatial and temporal variability (range=8–100 nM), and were supersaturated with respect to the atmosphere by a factor of 2–37. Rates of net water column CH₄ production-oxidation were determined by in situ experiments, and were not found to be significantly different from zero. Fluxes across the sediment-water interface, determined by direct measurement using benthic chambers, varied from ?0.1 μmol m^?2 d^?1 to +16 μmol m^?2 d^?1 (positive fluxes into water). Methane concentrations in the two perennial creeks feeding the bay varied annually (140–950 nM); these creeks were a significant CH₄ source to the bay during winter. In addition, mass-balance calculations indicate a significant additional inter CH₄ source, which is hypothesized to result from storm-related runoff from dairy farms adjacent to the bay. Systemwide CH₄ budgets of the 16-km² inner bay indicate benthic production (110 mol d^?1) and atmospheric evasion (110 mol d^?1) dominated during summer, while atmospheric evasion (160 mol d^?1) and runoff from dairy farms (90 mol d^?1) dominated during winter.     

Importance of submarine groundwater discharge as a source of nutrients for the Neuse River Estuary,North Carolina

Seepage rate and chemical composition of groundwater discharge entering the Neuse River Estuary (NRE) were quantified over an annual cycle from July 2005 through June 2006. Lee type seepage meters were deployed at eight locations within the NRE to quantify the amount of submerged groundwater discharge (SGD) entering the system. Sediment porewater nitrate (NO₃ ⁻), ammonium (NH₄ ⁺), and phosphate (PO₄ ⁻³) were also quantified at each of these locations to determine groundwater chemical composition. Seepage rates for the system ranged from 0.004 to 0.035 m³ m⁻² d⁻¹. Both the average and median value for the system-wide SGD were 0.01 m³ m⁻²d⁻¹. There were no significant differences between upstream and downstream seepage rates or between those at the north and south side of the estuary. Seepage rates varied greatly in time and space. Discharging groundwater was NO₃ ⁻ deplete but highly enriched in NH₄ ⁺. Porewater PO₄ ⁻³ levels varied but were usually present below Redfield values due to NH₄ ⁺ enrichment. SGD nutrient loading represented a small part of watershed nitrogen and phosphorus loading, 0.8% and 1.0%, respectively.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: I. Wet chemistry and aging effects

Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of Cs^I and Sr^II were studied in batch reactors of 2:1 layer-type silicates—illite (Il), vermiculite (Vm) and montmorillonite (Mt)—under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻³ mol kg⁻¹. Clay mineral type affected the rates of (i) hydroxide promoted dissolution of Si, Al and Fe, (ii) precipitation of secondary solids and (iii) uptake of Cs and Sr. Initial Si release to solution followed the order Mt > Vm > Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg⁻¹ (0.18, 0.24 and 0.02 μmol m⁻²) of Cs, and 0, 27 and 22 mmol kg⁻¹ (0, 0.14 and 0.03 μmol m⁻²) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.     

Adsorption and Desorption of Phosphate on Calcite and Aragonite in Seawater

The adsorption and desorption of phosphate on calcite and aragonite were investigated as a function of temperature (5–45 °C)and salinity (0–40) in seawater pre-equilibrated with CaCO₃. An increase in temperature increased the equilibrium adsorption; whereas an increase in salinity decreased the adsorption. Adsorption measurements made in NaCl were lower than the results in seawater. The higher values in seawater were due to the presence of Mg²⁺ and Ca²⁺ ions. The increase was 5 times greater for Ca²⁺ than Mg²⁺. The effects ofCa²⁺ and Mg²⁺ are diminished with the addition of SO₄ ^2- apparently due to the formation of MgSO₄ and CaSO₄ complexes in solution and/or SO₄ ^2- adsorption on the surface of CaCO₃. The adsorbed Ca²⁺ and Mg²⁺ on CaCO₃ (at carbonate sites) may act as bridges to PO₄ ^3- ions. The bridging effect of Ca²⁺is greater than Mg²⁺ apparently due to the stronger interactions of Ca²⁺ with PO₄ ^3-.The apparent effect of salinity on the adsorption of PO₄ was largely due to changes in the concentration of HCO₃ ^- in the solutions. An increase in the concentration of HCO₃ ^- caused the adsorption of phosphate to decrease, especially at low salinities. The adsorption at the same level of HCO₃ ^- (2 mM) was nearly independent of salinity. All of the adsorption measurements were modeled empirically using a Langmuir-type adsorption isotherm[ [PO₄]_ad = K_mC_m[PO₄]_T/(1 +K_m [PO₄]_T) , ]where [PO₄]_ad and [PO₄]_T are the adsorbed and total dissolved phosphate concentrations, respectively. The values of C_m (the maximum monolayer adsorption capacity, (mol/g) and K_m (the adsorption equilibrium constant, g/(mol) over the entire temperature (t, °C) and salinity (S) range were fitted to[ C_m = 17.067 + 0.1707t - 0.4693S + 0.0082S² ( = 0.7) ][ ln K_m = - 2.412 + 0.0165t - 0.0004St - 0.0008S² ( = 0.1) ]These empirical equations reproduce all of our measurements of[PO₄]_ad up to 14 mol/g and within ±0.7 mol/g.The kinetic data showed that the phosphate uptake on carbonate minerals appears to be a multi-step process. Both the adsorption and desorption were quite fast in the first stage (less than 30 min) followed by a much slower process (lasting more than 1 week). Our results indicate that within 24 hours aragonite has a higher sorption capacity than calcite. The differences between calcite and aragonite become smaller with time. Consequently, the mineral composition of the sediments may affect the short-term phosphate adsorption and desorption on calcium carbonate. Up to 80 % of the adsorbed phosphate is released from calcium carbonate over one day. The amount of PO₄ left on the CaCO₃ is close to the equilibrium adsorption. The release of PO₄ from calcite is faster than from aragonite. Measurements with Florida Bay sediments produced results between those for calcite and aragonite. Our results indicate that the calcium carbonate can be both a sink and source of phosphate in natural waters.     

Biogeochemical cycling in an organic-rich coastal marine basin—I. Methane sediment-water exchange processes

Methane produced in anoxic organic-rich sediments of Cape Lookout Bight, North Carolina, enters the water column via two seasonally dependent mechanisms: diffusion and bubble ebullition. Diffusive transport measured in situ with benthic chambers averages 49 and 163 μmol · m ^?2 · hr ^?1 during November–May and June–October respectively. High summer sediment methane production causes saturation concentrations and formation of bubbles near the sediment-water interface. Subsequent bubble ebullition is triggered by low-tide hydrostatic pressure release. June–October sediment-water gas fluxes at the surface average 411 ml (377 ml STP: 16.8 mmol) · m^?2 per low tide. Bubbling maintains open bubble tubes which apparently enhance diffusive transport. When tubes are present, apparent sediment diffusivities are 1.2–3.1-fold higher than theoretical molecular values reaching a peak value of 5.2 × 10^?5 cm² · sec^?1. Dissolution of 15% of the rising bubble flux containing 86% methane supplies 170μmol · m^?2 · hr^?1 of methane to the bight water column during summer months; the remainder is lost to the troposphere. Bottom water methane concentration increases observed during bubbling can be predicted using a 5–15 μm stagnant boundary layer dissolution model. Advective transport to surrounding waters is the major dissolved methane sink: aerobic oxidation and diffusive atmospheric evasion losses are minor within the bight.     

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.     

Nutrient-Replete Benthic Microalgae as a Source of Dissolved Organic Carbon to Coastal Waters

Dissolved organic carbon (DOC) flux dynamics were examined in the context of other biogeochemical cycles in intertidal sediments inhabited by benthic microalgae. In August 2003, gross oxygenic photosynthetic (GOP) rates, oxygen penetration depths, and benthic flux rates were quantified at seven sites along the Duplin River, GA, USA. Sediments contained abundant benthic microalgal (BMA) biomass with a maximum chlorophyll a concentration of 201 mg chl a m^?2. Oxygen microelectrodes were used to determine GOP rates and O₂ penetration depth, which were tightly correlated with light intensity. Baseline and ¹⁵N-nitrate amended benthic flux core incubations were employed to quantify benthic fluxes and to investigate the impact of BMA on sediment water exchange under nitrogen (N)-limited and N-replete conditions. Unamended sediments exhibited tight coupling between GOP and respiration and served as a sink for water column dissolved inorganic nitrogen (DIN) and a source of silicate and dissolved inorganic carbon (DIC). The BMA response to the N addition indicated sequential nutrient limitation, with N limitation followed by silicate limitation. In diel (light–dark) incubations, biological assimilation accounted for 83% to 150% of the nitrate uptake, while denitrification (DNF) and dissimilatory nitrate reduction to ammonium (DNRA) accounted for <7%; in contrast, under dark conditions, DNF and DNRA accounted for >40% of the NO₃ ^? uptake. The N addition shifted the metabolic status of the sediments from a balance of autotrophy and heterotrophy to net autotrophy under diel conditions, and the sediments served as a sink for water column DIN, silicate, and DIC but became a source of DOC, suggesting that the increased BMA production was decoupled from sediment bacterial consumption of DOC.     

Benthic Respiration and Inorganic Nutrient Fluxes in the Estuarine Region of Patos Lagoon (Brazil)

In situ benthic flux chamber experiments were performed during late austral spring and early summer of 1996 at eleven nearshore locations in the southern Patos Lagoon, Brazil. The Patos Lagoon is the largest lagoonal system in South America and is a very important nursery ground for local fin fish and shell fish fisheries. These are the first benthic flux measurements made in Patos Lagoon and they suggest that remineralizationwithin the sediments may dominate the recycling of organic matter and nutrients in thelagoon. Measured oxygen benthic fluxes (45–160 mmol m^-2 d^-1) are sufficientto remineralize reported mean water column carbon fixation while phosphate and fixednitrogen benthic fluxes (-0.4–2 and -1.1–4.2 mmol m^-2 d^-1, respectively)are sufficient to supply 100% and 25% of the required water column nutrient demand,respectively. Although of limited areal and temporal coverage, these initial studiesdemonstrate that sediments play a major role in the metabolism and nutrient cyclingwithin the Patos Lagoon Estuary and that future studies of lagoonal biogeochemistrymust consider exchange with the bottom.     

Non-conservative P and N fluxes and net ecosystem production in San Quintin Bay,México

San Quintin Bay, Mexico, is a hypersaline coastal lagoon where the main external forcing of physical and biogeochemical processes is oceanic. Non-conservative fluxes of inorganic N (ΔDIN) and P (ΔDIP), and aspects of net ecosystem metabolism were studied in this lagoon during August 1995, August 1996, and February 1996, by following the LOICZ budgetary modeling approach. The whole-system water exchange time during summer (≈13 d) was shorter than in winter (≈26 d) as northwesterly winds enhancing mixing with the ocean are more intense during the spring-summer upwelling season. Whole-bay ΔDIP values of +0.2 to +0.3 mmol m^?2 d^?1 in August, and <+0.01 mmol m^?2 d^?1 in February indicate that the system is a net source of dissolved inorganic phosphorus (DIP). DIP fluxes from the Bay to the ocean during August are probably balanced by a net import of particulate organic matter between 1,000–1,300 × 10³ mol C d^?1, equivalent to a net ecosystem production (NEP) between ?24 and ?31 mmol C m^?2 d^?1. ΔDIN showed opposite trends in August 1995 and August 1996, with a net import of 13×10³ mol N d^?1 and a net export of 30× 10³ mol N d^?1, respectively. However, N fixation minus denitrification (“apparent denitrification”) estimates of ≈?4 mmol N m^?2 d^?1 in both periods indicate that San Quintin Bay is a net sink of nitrogen. Results from a 3-box model indicate that during summer Box C, adjacent to the ocean, contributed 70–80% of the excess DIP produced in the whole-system. This observation and high apparent denitrification values of ≈?7 mmol N m^?2 d^?1 at the entrance of the Bay, suggest that the net heterotrophic condition of San Quintin Bay in summer is largely determined by imports of labile phytoplanktonic carbon generated in the adjacent ocean during upwelling.A net flux of organic carbon of 30×10⁶ mol C yr^?1 was estimated from Box C, adjacent to the ocean, to Box B, locally known as Bahia Falsa, which is the area designated for oyster aquaculture in the lagoon. It is estimated that this net organic carbon supply is almost equivalent to the annual oyster food demand; our estimate is that oyster aquaculture in San Quintin Bay accounts for the vast majority of the net heterotrophy of Bahia Falsa.