Redox cycling of iron and manganese in sediments of the Kalix River estuary, Northern Sweden

Iron and manganese redox cycling in the sediment — water interface region in the Kalix River estuary was investigated by using sediment trap data, pore-water and solid-phase sediment data. Nondetrital phases (presumably reactive Fe and Mn oxides) form substantial fractions of the total settling flux of Fe and Mn (51% of Fe_total and 84% of Mn_total). A steady-state box model reveals that nondetrital Fe and Mn differ considerably in reactivity during post-depositional redox cycling in the sediment. The production rate of dissolved Mn (1.6 mmol m^–2 d^–1) exceeded the depositional flux of nondetrital Mn (0.27 mmol m^–2 d^–1) by a factor of about 6. In contrast, the production rate of upwardly diffusing pore-water Fe (0.77 mmol m^–2 d^–1) amounted to only 22% of the depositional flux of nondetrital Fe (3.5 mmol m^–2 d^–1). Upwardly diffusing pore-water Fe and Mn are effectively oxidized and trapped in the oxic surface layer of the sediment, resulting in negligible benthic effluxes of Fe and Mn. Consequently, the concentrations of nondetrital Fe and Mn in permanently deposited, anoxic sediment are similar to those in the settling material. Reactive Fe oxides appear to form a substantial fraction of this buried, non-detrital Fe. The in-situ oxidation rates of Fe and Mn are tentatively estimated to be 0.51 and 0.16–1.7 mol cm^–3 d^–1, respectively.     

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.     

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.     

Nitrate sources and sinks in Elkhorn Slough,California: Results from long-term continuous in situ nitrate analyzers

Nitrate and water quality parameters (temperature, salinity, dissolved oxygen, turbidity, and depth) were measured continuously with in situ NO₃ analyzers and water quality sondes at two sites in Elkhorn Slough in Central California. The Main Channel site near the mouth of Elkhorn Slough was sampled from February to September 2001. Azevedo Pond, a shallow tidal pond bordering agricultural fields further inland, was sampled from December 1999 to July 2001. Nitrate concentrations were recorded hourly while salinity, temperature, depth, oxygen, and turbidity were recorded every 30 min. Nitrate concentrations at the Main Channel site ranged from 5 to 65 μM. The propagation of an internal wave carrying water from ≈100 m depth up the Monterey Submarine Canyon and into the lower section of Elkhorn Slough on every rising tide was a major source of nitrate, accounting for 80–90% of the nitrogen load during the dry summer period. Nitrate concentrations in Azevedo Pond ranged from 0–20 μM during the dry summer months. Nitrate in Azevedo Pond increased to over 450 μM during a heavy winter precipitation event, and interannual variability driven by differences in precipitation was observed. At both sites, tidal cycling was the dominant forcing, often changing nitrate concentrations by 5-fold or more within a few hours. Water volume flux estimates were combined with observed nitrate concentrations to obtain nitrate fluxes. Nitrate flux calculations indicated a loss of 4 mmol NO₃ m^?2 d^?1 for the entire Elkhorn Slough and 1 mmol NO₃ m^?2 d^?1 at Azevedo Pond. These results suggested that the waters of Elkhorn Slough were not a major source of nitrate to Monterey Bay but actually a nitrate sink during the dry season. The limited winter data at the Main Channel site suggest that nitrate was exported from Elkhorn Slough during the wet season. Export of ammonium or dissolved organic nitrogen, which we did not monitor, may balance some or all of the NO₃ flux.     

Benthic fluxes and the cycling of biogenic silica and carbon in two southern California borderland basins

Benthic fluxes in two southern California borderland basins have been estimated by modeling water column property gradients, by modeling pore water gradients and by measuring changes in concentration in a benthic chamber. Results have been used to compare the different methods, to establish budgets for biogenic silica and carbon and to estimate rate constants for models of CaCO₃ dissolution. In San Pedro Basin, a low oxygen, high sedimentation rate area, fluxes of radon-222 (86 ± 8 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.9 ± 0.3 mmol m⁻² d⁻¹) and nitrate (−0.8 ± 0.1 mmol m⁻² d⁻¹) measured in a benthic chamber agree within the measurement uncertainty with fluxes estimated from modeling profiles of nutrients and radon obtained in the water column. The diffusive fluxes of radon, SiO₂ and TCO₂ determined from modeling the sediment and pore water also agree with the other approaches. Approximately 33 ± 13% of the organic carbon and 37 ± 47% of the CaCO₃ arriving at the sea floor are recycled. In San Nicolas Basin, which has larger oxygen concentrations and lower sedimentation rates than San Pedro, the fluxes of radon (490 ± 16 atoms m⁻² s⁻¹), SiO₂ (0.7 ± 0.1 mmol m⁻² d⁻¹), alkalinity (1.7 ± 0.3 meq m⁻² d⁻¹), TCO₂ (1.7 ± 0.2 mmol m⁻² d⁻¹), oxygen (−0.7 ± 0.1 mmol m⁻² d⁻¹) and nitrate (-0.4 ± 0.1 mmol m⁻² d⁻¹) determined from chamber measurements agree with the water column estimates given the uncertainty of the measurements and model estimates. Diffusion from the sediments matches the lander-measured SiO₂ and PO₄³⁻ (0.017 ± 0.002 mmol m⁻² d⁻¹) fluxes, but is not sufficient to supply the radon or TCO₂ fluxes observed with the lander. In San Nicolas Basin 38 ± 9% of the organic carbon and 43 ± 22% of the CaCO₃ are recycled. Approximately 90% of the biogenic silica arriving at the sea floor in each basin is recycled. The rates of CaCO₃ dissolution determined from chamber flux measurements and material balances for protons and electrons are compared to those predicted by previously published models of CaCO₃ dissolution and this comparison indicates that in situ rates are comparable to those observed in laboratory studies of bulk sediments, but orders of magnitude less than those observed in experiments done with suspended sediments.     

The Effects of Salinity on Nitrogen Losses from an Oligohaline Estuarine Sediment

Benthic respiration, sediment–water nutrient fluxes, denitrification and dissimilatory nitrate reduction to ammonium (DNRA) were measured in the upper section of the Parker River Estuary from 1993 to 2006. This site experiences large changes in salinity over both short and long time scales. Sediment respiration ranged from 6 to 52 mmol m⁻² day⁻¹ and was largely controlled by temperature. Nutrient fluxes were dominated by ammonium fluxes, which ranged from a small uptake of −0.3 to an efflux of over 8.2 mmol N m⁻² day⁻¹. Ammonium fluxes were most highly correlated with salinity and laboratory experiments demonstrated that ammonium fluxes increased when salinity increased. The seasonal pattern of DNRA closely followed salinity. DNRA rates were extremely low in March, less than 0.1 mmol m⁻² day⁻¹, but increased to 2.0 mmol m⁻² day⁻¹ in August. In contrast, denitrification rates were inversely related to salinity, ranging from 1 mmol m⁻² day⁻¹ during the spring and fall to less than 0.2 mmol m⁻² day⁻¹ in late summer. Salinity appears to exert a major control on the nitrogen cycle at this site, and partially decouples sediment ammonium fluxes from organic matter decomposition.     

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.     

Exchange of polychlorinated biphenyls between sediment and water in the Hudson River estuary

Sediment-bound polychlorinated biphenyls (PCBs) measured at several sites in the lower Hudson River Estuary are above equilibrium with the overlying water, providing a thermodynamic driving force for exchange from sediment to water. The fluxes of PCB congeners are estimated for a number potential processes: diffusive release of dissolved and colloidal PCBs from the bed, resuspension and subsequent desorption from resuspended particles, and sediment accumulation and burial. All processes are potentially significant, at least for some congeners. The sediment exchange fluxes of PCB solutes for five sites between Governors Island and Haverstraw Bay are estimated to be 20–860 μm m^?2 d^?1, which is between 2 and 100 times more than the flux of dissolved PCBs coming down the river at Haverstraw Bay. Much of the exchange from sediment to water may be balanced by burial of sorbed PCBs by sediment accumulation. Advection down the river and sediment exchange dominate other potential sources of PCBs to the lower estuary under current loading conditions. The magnitude of the calculated fluxes is consistent with the nonconservative behavior of PCBs in the same region but is higher than earlier modeling estimates that employed different assumptions.     

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.     

Amino acid composition of suspended particles,sediment-trap material,and benthic sediment in the Potomac Estuary

Sediment trap deployments in estuaries provide a method for estimating the amount of organic material transported to the sediments from the euphotic zone. The amino acid composition of suspended particles, benthic sediment, and sediment-trap material collected at 2.4 m, 5.8 m, and 7.9 m depths in the Potomac Estuary was determined in stratified summer waters, and in well-mixed oxygenated waters (DO) in late fall. The total vertical flow, or flux, of material into the top traps ranged from 3 g m^?2 d^?1 in August to 4.9 g m^?2 d^?1 in October. The carbon and nitrogen fluxes increased in the deepest traps relative to the surface traps during both sampling periods, along with that of the total material flux (up to 47.3 g m^?2 d^?1 in the deepest trap), although the actual weight percent of organic carbon and organic nitrogen decreased with depth. Amino acid concentrations ranged from 129 mg g^?1 in surface water particulate material to 22 mg g^?1 in particulate material in 9-m-deep waters and in the benthic sediment. Amino acid concentrations from 2.4-mg-depth sediment traps averaged 104±29 mg g^?1 in stratified waters and 164±81 mg g^?1 in well-mixed waters. The deep trap samples averaed, 77.3±4.8 mg g^?1 amino acids in summer waters and 37±16 mg g^?1 in oxygenated fall waters. Amino acids comprised 13% to 39% of the organic carbon and 12% to 89% of the orgnaic nitrogen in these samples. Analysis of the flux results suggest that resuspension combined with lateral advection from adjacent slopes can account for up to 27% of the material in the deep traps when the estuary was well-mixed and unstratified. When the estuary was stratified in late summer, the amino acid carbon produced by primary productivity in the euphotic zone decreased by 85% (86% for total organic carbon) at the pycnocline at 6 m depth, leaving up to 15% of the vertical organic flux available for benthic sediment deposition.     

Benthic Phosphorus Dynamics in the Gulf of Finland, Baltic Sea

Benthic fluxes of soluble reactive phosphorus (SRP) and dissolved inorganic carbon (DIC) were measured in situ using autonomous landers in the Gulf of Finland in the Baltic Sea, on four expeditions between 2002 and 2005. These measurements together with model estimates of bottom water oxygen conditions were used to compute the magnitude of the yearly integrated benthic SRP flux (also called internal phosphorus load). The yearly integrated benthic SRP flux was found to be almost 10 times larger than the external (river and land sources) phosphorus load. The average SRP flux was 1.25?±?0.56?mmol?m^?2?d^?1 on anoxic bottoms, and ?0.01?±?0.08?mmol?m^?2?d^?1 on oxic bottoms. The bottom water oxygen conditions determined whether the SRP flux was in a high or low regime, and degradation of organic matter (as estimated from benthic DIC fluxes) correlated positively with SRP fluxes on anoxic bottoms. From this correlation, we estimated a potential increase in phosphorus flux of 0.69?±?0.26?mmol?m^?2?d^?1 from presently oxic bottoms, if they would turn anoxic. An almost full annual data set of in situ bottom water oxygen measurements showed high variability of oxygen concentration. Because of this, an estimate of the time which the sediments were exposed to oxygenated overlying bottom water was computed using a coupled thermohydrodynamic ocean?Csea and ecosystem model. Total phosphorus burial rates were calculated from vertical profiles of total phosphorus in sediment and sediment accumulation rates. Recycling and burial efficiencies for phosphorus of 97 and 3%, respectively, were estimated for anoxic accumulation bottoms from a benthic mass balance, which was based on the measured effluxes and burial rates.     

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.     

Spatial and Temporal Variability of Benthic Respiration in a Scottish Sea Loch Impacted by Fish Farming: A Combination of In Situ Techniques

The effects of fish farm activities on sediment biogeochemistry were investigated in Loch Creran (Western Scotland) from March to October 2006. Sediment oxygen uptake rates (SOU) were estimated along an organic matter gradient generated from an Atlantic salmon farm using a combination of in situ techniques: microelectrodes, planar optode and benthic chamber incubations. Sulphide (H₂S) and pH distributions in sediment porewater were also measured using in situ microelectrodes, and dissolved inorganic carbon (DIC) fluxes were measured in situ using benthic chambers. Relationships between benthic fluxes, vertical distribution of oxidants and reduced compounds in the sediment were examined as well as bacterial abundance and biomass. Seasonal variations in SOU were relatively low and mainly driven by seasonal temperature variations. The effect of the fish farm on sediment oxygen uptake rate was clearly identified by higher total and diffusive oxygen uptake rates (TOU and DOU, respectively) on impacted stations (TOU: 70 ± 25 mmol O₂ m^?2 day^?1; DOU: 70 ± 32 mmol O₂ m^?2 day^?1 recalculated at the summer temperature), compared with the reference station (TOU: 28.3 ± 5.5 mmol O₂ m^?2 day^?1; DOU: 21.5 ± 4.5 mmol O₂ m^?2 day^?1). At the impacted stations, planar optode images displayed high centimetre scale heterogeneity in oxygen distribution underlining the control of oxygen dynamics by small-scale processes. The organic carbon enrichment led to enhanced sulphate reduction as demonstrated by large vertical H₂S concentration gradients in the porewater (from 0 to 1,000 μM in the top 3 cm) at the most impacted site. The impact on ecosystem functions such as bioirrigation was evidenced by a decreasing TOU/DOU ratio, from 1.7 in the non-impacted sediments to 1 in the impacted zone. This trend was related to a shift in the macrofaunal assemblage and an increase in sediment bacterial population. The turnover time of the organic load of the sediment was estimated to be over 6 years.     

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.     

Anaerobic diagenesis of silica and carbon in continental margin sediments: Discrete zones of TCO2 production

Pore water profiles of dissolved Si, Ca²⁺, SO₄^2-, CH₄, and TCO₂ (Dissolved Inorganic Carbon; DIC) were determined from multicores and gravity cores collected at nine sites off Southern California, the west coast of Mexico, and within the Gulf of California. These sites were located within the eastern North Pacific oxygen minimum zone at depths of 400 to 900 m and in settings where bottom water oxygen concentrations were <3 μM and sediments were laminated. Pore water profiles were defined at a resolution of millimeters (whole core squeezing), centimeters (sectioning and squeezing) and meters (gravity core sectioning and squeezing), and diffusive fluxes were calculated for different zones within the sediment column. The flux of dissolved silica across the sediment-water interface (SWI) ranged from 0.3 to 3.4 mmol Si m^-2d^-1, and TCO₂ fluxes ranged from 0.8 to 4.6 mmol C m^-2d^-1. A positive correlation (r = 0.74) existed between these fluxes, yet these two constituents exhibited significantly different diagenetic behavior downcore; dissolved Si generally reached a constant concentration (between 450 and 900 μM) in the upper few cm, whereas TCO₂ concentrations increased monotonically with depth.Methane was detected at micromolar levels in sediment intervals between 0 and 60 cm and at five sites, increased to millimolar levels at depths of 80 to 170 cm. At the horizon marking the appearance of millimolar levels of methane, there was a distinct change in slope of the sulfate and TCO₂ gradients. A flux budget for this horizon was determined by using linear fits to pore water profiles; these budgets indicate that the upward TCO₂ flux away from this horizon is 40 to 50% greater than the downward sulfate flux to this horizon. Given that the TCO₂ flux to this horizon from below was quite small, this imbalance suggests that anaerobic oxidation of methane by sulfate is not the only process producing TCO₂ within this horizon. A budget for TCO₂ at this horizon is balanced when 40 to 80% of the sulfate flux is attributed to organic carbon remineralization. Of the DIC that diffuses across the SWI, 20 to 40% is generated by reactions occurring within or below this deep reaction horizon.     

Behavior of arsenic and antimony in the surface freshwater reaches of a highly turbid estuary, the Gironde Estuary, France

This study reports on the behavior of two redox-sensitive elements, As and Sb, along the turbidity gradient in the freshwater reaches of the turbid Gironde Estuary. During a 17-month survey, surface water and suspended particulate matter (SPM) were sampled monthly at six sites representing both fluvial branches of the Gironde Estuary. Additionally, two longitudinal high resolution profiles were sampled along the fluvial estuary of the Garonne Branch during two contrasted seasons, i.e. with and without the presence of the maximum turbidity zone (MTZ). Seasonal variability and spatial distribution of dissolved (<0.2 μm; <0.02 μm) and particulate As, Sb and Fe were measured and combined with SPM data to understand metalloid behavior in the estuarine freshwater turbidity gradient.At the two main fluvial entries of the Gironde Estuary, dissolved As and Sb concentrations showed strong (by a factor of 2–4) seasonal variations, that were only partly controlled by discharge-related dilution. Seasonal addition of dissolved As and Sb was attributed to the degradation of particulate As and Sb carrier phases in bottom sediment and/or in the adjacent aquifers, rather than release from SPM. In the surface freshwater reaches of the Gironde Estuary, Sb behaved conservatively under all hydrological conditions. In contrast, As was strongly reactive in the presence of the MTZ, with opposite behaviors in the two fluvial branches of the estuary: in the Garonne Branch As was removed from the dissolved phase, whereas in the Dordogne Branch As was added. Redistribution of As between the dissolved and the particulate phases along the turbidity gradient in estuarine freshwater only affected the <0.02 μm fraction, as the 0.02–0.2 μm fraction remained constant (300 ng L⁻¹ in September 2005). Accordingly, As removal seemed to be decoupled from concomitant “colloidal” (0.02–0.2 μm) Fe flocculation in the turbidity gradient. The contrasting behavior of dissolved As in the fluvial estuaries of the Garonne and Dordogne Branches was attributed to sorption processes during equilibration of river-borne dissolved As with estuarine SPM forming the MTZ. This equilibrium, described by a distinct distribution coefficient K_d(As)  11,000 L kg⁻¹ in the MTZ, resulted in either As release (desorption; Dordogne Branch) or removal (adsorption; Garonne Branch) in the respective fluvial estuaries. A mixing experiment under controlled laboratory conditions tended to support that equilibration between the dissolved phase and MTZ particles may induce both As release and removal in the estuarine freshwater reaches, with As distribution evolving towards a distinct K_d value for increasing SPM concentrations. The long-term survey allowed estimating annual (2004) dissolved fluxes of As and, for the first time Sb, at the main fluvial entries of the Gironde Estuary at 30.7 t a⁻¹ and 3.2 t a⁻¹ (Garonne River) and at 8.0 t a⁻¹ and 2.3 t a⁻¹ (Dordogne River), respectively.     

Primary production in Long Island sound

Daily and annual integrated rates of primary productivity and community respiration were calculated using physiological parameters measured in oxygen-based photosynthesis-irradiance (P-I) incubations at 8 stations throughout central and western Long Island Sound (cwLIS) during the summer and autumn of 2002 and 2003 and the late spring of 2003. Each calculation takes into account actual variations in incident irradiance over the day and underwater irradiance and standing stock with depth. Annual peak rates, ±95% confidence interval of propagated uncertainty in each measurement, of gross primary production (GPP, 1,730±610 mmol O₂ m⁻² d⁻¹), community respiration (R_c, 1,660±270 mmol O₂ m⁻² d⁻¹), and net community production (NCP, 1,160±1,100 mmol O₂ m⁻² d⁻¹) occurred during summer at the western end of the Sound. Lowest rates of GPP (4±11 mmol O₂ m⁻² d⁻¹), R_c (−50±300 mmol O₂ m⁻² d⁻¹), and NCP (−1,250±270 mmol O₂ m⁻² d⁻¹) occurred during late autumn-early winter at the outer sampled stations. These large ranges in rates of GPP, R_c, and NCP throughout the photic zone of cwLIS are attributed to seasonal and spatial variability. Algal respiration (R_a) was estimated to consume an average of 5% to 52% of GPP, using a literature-based ratio of R_a:R_c. From this range, we established that the estimated R_a accounts for approximately half of GPP, and was used to estimate daily net primary production (NPP), which ranged from 2 to 870 mmol O₂ m⁻² d⁻¹ throughout cwLIS during the study. Annual NPP averaged 40±8 mol O₂ m⁻² yr⁻¹ for all sampled stations, which more than doubled along the main axis of the Sound, from 32±14 mol O₂ m⁻² yr⁻¹ at an eastern station to 82±25 mol O₂ m⁻² yr⁻¹ at the western-most station. These spatial gradients in productivity parallel nitrogen loads along the main axis of the Sound. Daily integrals of productivity were used to test and formulate a simple, robust biomass-light model for the prediction of phytoplankton production in Long Island Sound, and the slope of the relationship was consistent with reports for other systems.     

Calcite dissolution driven by benthic mineralization in the deep-sea: in situ measurements of Ca2+, pH,pCO2 and O2

In situ measured microprofiles of Ca²⁺, pCO₂, pH and O₂ were performed to quantify the CaCO₃ dissolution and organic matter mineralization in marine sediments in the eastern South Atlantic. A numerical model simulating the organic matter decay with oxygen was used to estimate the calcite dissolution rate. From the oxygen microprofiles measured at four stations along a 1300-m isobath of the eastern African margin and one in front of the river Niger at a water depth of 2200 m the diffusive oxygen uptake (DOU) and oxygen penetration depth (OPD) was calculated. DOU rates were in the range of 0.3 to 3 mmol m⁻² d⁻¹ and showed a decrease with increasing water depth, corresponding to an increase in OPD. The calculated amount of degradated organic matter is in the range of 1 to 8.5 gC m⁻² a⁻¹. The metabolic CO₂, released from mineralization of the organic matter drives calcite dissolution in these sediments overlain by calcite-supersaturated water. Fluxes across the sediment water interface calculated from the in situ Ca²⁺ microprofiles were 0.6 mmol m⁻² d⁻¹ for two stations at a water depth of 1300 m. The ratio of calcite dissolution flux and organic C degradation is 0.53 and 0.97, respectively. The microprofiles indicate that CO₂ produced within the upper oxic sediment layer dissolves up to 85% of the calcite rain to the seafloor. Modeling our O₂, pH and Ca²⁺ profiles from one station predicted a calcite dissolution rate constant for this calcite-poor site of 1000 mol kgw⁻¹ a⁻¹ (mol per kg water and year), which equals 95% d⁻¹. This rate constant is at the upper end of reported in situ values.     

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.     

The Dynamics of Benthic Respiration at a Mid-Shelf Station Off Oregon

Mid-shelf sediments off the Oregon coast are characterized as fine sands that trap and remineralize phytodetritus leading to the consumption of significant quantities of dissolved oxygen. Sediment oxygen consumption (SOC) can be delayed from seasonal organic matter inputs because of a transient buildup of reduced constituents during periods of quiescent physical processes. Between 2009 and 2013, benthic oxygen exchange rates were measured using the noninvasive eddy covariance (EC) method five separate times at a single 80-m station. Ancillary measurements included in situ microprofiles of oxygen at the sediment–water interface, and concentration profiles of pore water nutrients and trace metals, and solid-phase organic C and sulfide minerals from cores. Sediment cores were also incubated to derive anaerobic respiration rates. The EC measurements were made during spring, summer, and fall conditions, and they produced average benthic oxygen flux estimates that varied between ?2 and ?15 mmol m^?2 d^?1. The EC oxygen fluxes were most highly correlated with bottom-sensed, significant wave heights (H _s). The relationship with H _s was used with an annual record of deepwater swell heights to predict an integrated oxygen consumption rate for the mid-shelf of 1.5 mol m^?2 for the upwelling season (May–September) and 6.8 mol m^?2 y^?1. The annual prediction requires that SOC rates are enhanced in the winter because of sand filtering and pore water advection under large waves, and it counters budgets that assume a dominance of organic matter export from the shelf. Refined budgets will require winter flux measurements and observations from cross-shelf transects over multiple years.