Particle–water interactions of 2,2′,5,5′-tetrachlorobiphenyl under simulated estuarine conditions

A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, K_D, decreased from about 120×10³ to 10×10³ ml g⁻¹, and from about 150×10³ to 20×10³ ml g⁻¹, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l⁻¹. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds.     

The solubility of CaCO3 in seawater at 2°C based upon in-situ sampled pore water composition

Analyses of the concentration product (Ca²⁺) × (CO₃²⁻) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′_SPc) and aragonite (K′_SPa) in seawater. Regression of the data gives the relation In K′^P_SPc = 1.94 × 10⁻³ δP − 14.59 The 2°C, 1 atm value of K′_SPc is, then, 4.61 × 10⁻⁷ mol² l⁻². The pressure coefficient yields a at 2°C of −43.8 cm³ atm⁻¹. A single station where aragonite is present in the sediments gives a value of K′_SPa = 9.2 × 10⁻⁷ (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′_SPc at 2°C and 1 atm. The calculated is also indistinguishable from the experimental results of Ingle (1975) if is assumed to be independent of pressure.     

Copper complexing capacity of phytoplanktonic cell exudates

Copper complexing capacity of cell exudates of Dunaliella salina in natural seawater culture medium was investigated in order to evaluate the influence of this organism on speciation of trace metals in seawater.Seawater samples were collected at 200 m and 2 miles off the coast and immediately filtered. Copper complexing capacity (CC_Cu) and stability constants (K′) of related cupric complexes were then measured. They were, respectively, 27.1 × 10⁻⁸ mol l⁻¹ and 0.56 × 10⁷ l mol⁻¹ for the samples collected at 200 m and 12.8 × 10⁻⁸ mol l⁻¹ and 6.10 × 10⁷ l mol⁻¹ for those collected 2 miles off the coast. A stock culture (20 ml, 10⁶ cells ml⁻¹) in log-phase was inoculated in 2 l of each sample of filtered natural seawater. The trend of cell influence was estimated on filtered culture medium by measuring CC_Cu and K′ after 1 h, 3 and 7 days. From the results it appears that CC_Cu increased with respect to time and this was related to the growth rate, indicating a certain relationship with cell metabolic activity.It can be concluded that a comparison between the culture referring to 200 m and 2 miles, respectively, shows that the former presents a CC_Cu two times higher than the latter while the K′ is ten times higher at 2 miles than that at 200 m.     

Sorption model for dissolved and particulate aluminium in the Conway estuary, UK

Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, K_d, which varies from 0.67 × 10⁵ to 3.38 × 10⁶ ml g⁻¹ for suspended particle concentrations of 2–64 mg l⁻¹. The K_d values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for K_d values of 10⁵, 10⁶ and 10⁷ ml g⁻¹ with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with K_d value 10⁷ ml g⁻¹ and C₀ values 16 × 10⁻⁶ mg ml⁻¹ and 92 × 10⁻⁶ mg ml⁻¹. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries.     

Kinetic and equilibrium studies of copper-dissolved organic matter complexation in water column of the stratified Krka River estuary (Croatia)

An interaction of dissolved natural organic matter (DNOM) with copper ions in the water column of the stratified Krka River estuary (Croatia) was studied. The experimental methodology was based on the differential pulse anodic stripping voltammetric (DPASV) determination of labile copper species by titrating the sample using increments of copper additions uniformly distributed on the logarithmic scale. A classical at-equilibrium approach (determination of copper complexing capacity, CuCC) and a kinetic approach (tracing of equilibrium reconstitution) of copper complexation were considered and compared. A model of discrete distribution of organic ligands forming inert copper complexes was applied. For both approaches, a home-written fitting program was used for the determination of apparent stability constants (K_i^equ), total ligands concentration (L_iT) and association/dissociation rate constants (k_i¹,k_i^- 1).A non-conservative behaviour of dissolved organic matter (DOC) and total copper concentration in a water column was registered. An enhanced biological activity at the freshwater–seawater interface (FSI) triggered an increase of total copper concentration and total ligand concentration in this water layer. The copper complexation in fresh water of Krka River was characterised by one type of binding ligands, while in most of the estuarine and marine samples two classes of ligands were identified. The distribution of apparent stability constants (log K₁^equ: 11.2–13.0, log K₂^equ:8.8–10.0) showed increasing trend towards higher salinities, indicating stronger copper complexation by autochthonous seawater organic matter.Copper complexation parameters (ligand concentrations and apparent stability constants) obtained by at-equilibrium model are in very good accordance with those of kinetic model. Calculated association rate constants (k₁¹:6.1–20 × 10³ (M s)^− 1, k₂¹: 1.3–6.3 × 10³ (M s)^− 1) indicate that copper complexation by DNOM takes place relatively slowly. The time needed to achieve a new pseudo-equilibrium induced by an increase of copper concentration (which is common for Krka River estuary during summer period due to the nautical traffic), is estimated to be from 2 to 4 h.It is found that in such oligotrophic environment (dissolved organic carbon content under 83 µM_C, i.e. 1 mg_CL^− 1) an increase of the total copper concentration above 12 nM could enhance a free copper concentration exceeding the level considered as potentially toxic for microorganisms (10 pM).     

Investigations of iron coordination and redox reactions in seawater using Fe radiometry and ion-pair solvent extraction of amphiphilic iron complexes

Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using ⁵⁹Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 10⁶M⁻¹s⁻¹ and 20 M⁻¹s⁻¹, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)₃^o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands.     

Modelling the manganese cycling in two stratified fjords

This paper presents a parameterized model for the particulate and dissolved manganese profiles in two stratified fjords. Rates of oxidation and reduction of manganese are of the order of 1.0 × 10⁻¹⁵ mol cm⁻³ s⁻¹. Oxidation of manganese is probably not promoted by an inorganic surface-catalyzed reaction. Cycling of manganese in the redoxcline is extensive (10–100 cycles) and is related to the input of manganese to the fjords. Calibration of the model against sediment-trap-data allow instantaneous eddy diffusion coefficients to be estimated. These are of the order of 0.01 and 1.0 × 10⁻⁴ cm² s⁻¹.     

Solvent extraction of copper acetylacetonate in studies of copper(II) speciation in seawater

A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K₁ = 1.2 × 10¹², C_L1 = 5.1 × 10⁻⁹ M; type 2, K₂ = 2.8 × 10¹⁰, C_L2 = 1.1 × 10⁻⁷ M. Speciation is dominated by ligand type 1. Depth profiles of [Cu(II)]_free/[Cu(II)]_total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10⁻⁵ at 50–60 m to > 1 × 10⁻³ at the surface at two stations off the Florida coast.     

Apparent copper complexation capacity and conditional stability constants in north atlantic waters

Surface water samples were collected in the north Atlantic Ocean in July–August 1983. Their apparent complexation capacity for copper (CC_Cu) was determined on board, using differential pulse anodic stripping voltammetry under clean room conditions. Measurements were carried out by direct titrations as well as after equilibration of copper spikes. CC_Cu and conditional stability constants (K′) were calculated, by means of three different methods, which are compared.On the basis of salinity, temperature, silicate and phosphate concentrations the following surface waters could be distinguished: North Atlantic Drift (I), East Greenland Current (II), Labrador Current (III) and Gulf Stream waters (IV, V). CC_Cu and K′ were found to differ between these waters. The range of values for CC_Cu and their mean values given in parentheses, as calculated from van den Berg plots for waters I–IV are: I, 53–65 (59); II, 47–66 (55); III, 37–53 (45); IV, 20–42 (33) nM Cu. The range and mean values for log K′ are: I, 8.23–8.33 (8.28); II, 7.89–8.11 (7.98); III, 8.40–8.41 (8.41); IV, 7.90–8.21 (8.06).Information on complexation kinetics extracted from the titration curve revealed that k_f^′ is area-specific. The complexation rate constant in the northern part (Area I) is about two times larger than that in the southern area IV, (3.6 ± 0.3) and (2.2 ± 0.2) × 10⁴s⁻¹M⁻¹ Cu, respectively.Preliminary results for deep water samples suggest smaller but still existent CC_Cu and higher K′ than those found for surface waters.     

Shear and Richardson number in a mode-water eddy

Measurements of stratification and shear were carried out as part of the EDDIES tracer release experiment in mode-water eddy A4 during the summer of 2005. These measurements were accomplished using both shipboard instrumentation and a drifting mooring. A strong relationship between shear intensity and distance from the center of the eddy A4 was observed with the shipboard ADCP. Diapycnal diffusivity at the SF₆ tracer isopycnal prior to and during the release was estimated from the drifting mooring to be 2.9×10⁻⁶ m² s⁻¹. Diffusivity increased by an order of magnitude to 3.2×10⁻⁵ m² s⁻¹ during the period of the final tracer survey in early September, which was similar to the value estimated from the tracer analysis for the whole experiment (3.5×10⁻⁵ m² s⁻¹, [Ledwell, J.R., McGillicuddy Jr., D.J., Anderson, L.A., 2008. Nutrient flux into an intense deep chlorophyll layer in a mode-water eddy. Deep-Sea Research II, this issue [doi:10.1016/j.dsr2.2008.02.005]].     

Non-conservative Nutrient Fluxes from Budgets for the Irish Sea

Budgets for conservative tracers are used to determine the flow through the Irish Sea and combined with available data on nutrient distributions and inputs to estimate non-conservative nutrient fluxes. Steady state salinity and caesium-137 balances yield consistent estimates of the flow through the Irish Sea of Φ≈6×10⁴ m³s⁻¹. Using both tracers together with a mass balance allows the inclusion of separate diffusive flux terms and results in a diffusivity estimate ofK≈450 m²s⁻¹and a reduced flow of Φ≈4×10⁴ m³s⁻¹. These values are, however, sensitive to the gradients of salinity and caesium-137 concentration, which are not well defined by the observations.Following the LOICZ procedures, salinity and mass balances were combined with analogous statements for dissolved inorganic phosphorus (DIP) and dissolved inorganic nitrogen (DIN), in order to assess the non-conservative process rates. With regard to phosphorus it was found that the Irish Sea is close to balance with a slight net uptake of dissolved inorganic phosphorus, but the implied excess of uptake over release is not significant on account of uncertainties in the observations of boundary values and inputs. The DIN budget is subject to comparable uncertainties in the input data but does, however, indicate a significant imbalance with an average rate of denitrification of the order 0·3 mol N m⁻²y⁻¹.The implications of these budget results and their limitations are considered in relation to the application of the budgeting approach to areas with sparse data coverage. While the application of box model disciplines to conservative tracers can lead to satisfactory estimates of advective transport, the extension to non-conservative components requires extensive data to adequately specify the boundary values and input parameters averaged over the seasonal cycle.     

Interaction of cadmium and copper with surface-active organic matter and complexing ligands released by marine phytoplankton

The organic matter released by the marine phytoplankton species Dunaliella tertiolecta and its physico-chemical interaction with cadmium and copper ions were studied by electrochemical methods (differential pulse anodic stripping voltammetry (DPASV) and a.c. polarography). The interactions with cadmium and copper were studied at the model interface (mercury electrodesolution) and in the bulk phase by measuring the complexing ability of the released organic material.The axenic cultures were grown on different growth media, without and with trace metals and chelators. Culture media were analyzed 10 days after inoculation, containing 5 × 10⁵−1.2 × 10⁶ cells cm⁻³ when untreated or after separation of cells by gentle centrifugation.It was found that the content and type of the released surface-active material and complexing ligands depend on the initial composition of the growth media. In all cases, strong interaction of excreted organic substances with copper in the bulk phase and with cadmium at the model interface were observed.A rather high value of the complexing capacity, 9.5 × 10⁻⁷ mol Cu²⁺ dm⁻³, was found in the culture grown on medium without trace metals and chelators (medium I) whereas the surface activity of this culture was not high (0.2 mg dm⁻³ equivalent to Triton-X-100). Higher contents of surface-active material (0.8 and 1.0 mg dm⁻³) were found in cultures grown in media with trace metals and without chelators (II and III), accompanied by a high content of complexing ligands (5.8 × 10⁻⁷ and 9.5 × 10⁻⁷ mol Cu²⁺ dm⁻³). However, if the complexing capacity is calculated per cell the values obtained for cultures grown in media II and III (0.79 × 10⁻¹⁵ and 0.98 × 10⁻¹⁵ mol Cu²⁺ dm⁻³) are lower than for cultures grown on medium I (1.8 × 10⁻¹⁵ mol Cu²⁻ dm⁻³). The exceptional adsorption effects and the copper complexing capacity for medium 1, and the presence of cells with degenerative symptoms can be ascribed to stressed growth conditions, and, particularly, to deficiency of metals. A qualitatively similar behaviour has been observed in natural samples of estuarine waters, indicating the existence of stressed conditions during the mixing of fresh and saline waters.     

Variability in plankton community structure, metabolism, and vertical carbon fluxes along an upwelling filament (Cape Juby, NW Africa)

The variability in dissolved and particulate organic matter, plankton biomass, community structure and metabolism, and vertical carbon fluxes were studied at four stations (D₁–D₄), placed along a coastal-offshore gradient of an upwelling filament developed near Cape Juby (NW Africa). The filament was revealed as a complex and variable system in terms of its hydrological structure and distribution of biological properties. An offshore shift from large to small phytoplankton cells, as well as from higher to lower autotrophic biomass, was not paralleled by a similar gradient in particulate (POC) or dissolved (DOC) organic carbon. Rather, stations in the central part of the filament (D₂ and D₃) presented the highest organic matter concentrations. Autotrophic carbon (POC_Chl) accounted for 53% (onshore station, D₁) to 27% (offshore station, D₄) of total POC (assuming a carbon to chlorophyll ratio of 50), from which nano- and pico-phytoplankton biomasses (POC_{A < 10 μm}) represented 14% (D₁) to 79% (D₄) of POC_Chl. The biomass of small hetrotrophs (POC_{H < 10 μm}) was equivalent to POC_{A < 10 μm}, except at D₁, where small autotrophs were less abundant. Dark community respiration (R_d) in the euphotic zone was in general high, almost equivalent to gross production (P_g), but decreasing offshore (D₁–D₄, from 108 to 41 mmol C m⁻² d⁻¹). POC sedimentation rates (POC_sed) below the euphotic zone ranged from 17 to 6 mmol C m⁻² d⁻¹. Only at D₄ was a positive carbon balance observed: P_g−(R_d + POC_sed) = 42 mmol C m⁻² d⁻¹. Compared to other filament studies from the NE Atlantic coast, the Cape Juby filament presented lower sedimentation rates and higher respiration rates with respect to gross production. We suggest that this is caused by the recirculation of the filament water, induced by the presence of an associated cyclonic eddy, acting as a trapping mechanism for organic matter. The export capacity of the Cape Juby filament therefore would be constrained to the frequency of the interactions of the filament with island-induced eddies.     

Ten-year observation of the Gironde tributary fluvial system: fluxes of suspended matter, particulate organic carbon and cadmium

A program of long-term observation of suspended solids (TSS), particulate organic carbon (POC) and cadmium transported into the Gironde estuary (France) by its major tributaries has been carried out between 1990 and 1999. This decade included contrasting hydrologic cycles and appears representative of a much longer period (1959–1999). The Garonne and the Dordogne river systems are the main tributaries of the Gironde estuary and derive their waters from drainage basins with different geological, industrial and agricultural features. To better understand their respective contributions, they have been observed separately and compared. Water and TSS fluxes of the Garonne River show greater temporal variations and discharge is more related to the hydrology of the drainage basin (e.g. wet/dry years, local flood events etc.). As POC and particulate Cd concentrations in suspended matter are much less variable than turbidity, their fluxes are mainly controlled by the TSS transport. A major part of annual fluxes of TSS and associated pollutants may occur within few flood days (depending on various parameters, e.g. intensity, duration, season, etc.), and also the succession of dry and wet years has an important influence on annual fluxes. The presented data allow calculating fluvial inputs into the Gironde as the sum of fluxes transported by its major tributaries, the Garonne and the Dordogne river systems. Mean annual fluxes into the Gironde observed in 1990–1999 are about 34×10⁹ m³ year⁻¹ for river water, 3.24×10⁶ t year⁻¹ for suspended solids (TSS) and 9.88×10⁹ mol year⁻¹ for particulate organic carbon (POC). Generally, these fluxes are dominated by the contributions of the Garonne River. However, in dry years, the mean contribution of the Dordogne river system (including Dronne and Isle rivers) to the POC input into the estuary exceeded that of the Garonne. This reflects significant differences in vegetation and soil due to natural properties and land management of the basins. Mean Cd fluxes into the estuary are about 110×10³ mol year⁻¹ of which 19.6×10³ mol year⁻¹ are transported in the dissolved and 90.8×10³ mol year⁻¹ in the particulate phases, respectively. In 1991 (dry year), the net (dissolved) Cd flux towards the ocean exceeded the gross fluvial input of total Cd, suggesting the release of Cd from an important stock in the maximum turbidity zone (MTZ) or the fluid mud of the Gironde estuary.     

Meridional carbon dioxide transport in the northern North Atlantic

Combination of estimated water transport and accurate measurements of total carbon dioxide (TCO₂) on a hydrographic section at 58 °N allows the assessment of meridional inorganic carbon transport in the northern North Atlantic Ocean. The transport has been decomposed into contributions from the large-scale baroclinic overturning, the Ekman transport, baroclinic and a barotropic eddy terms, and an estimated contribution of the East Greenland Current. These terms are −0.27 · 10⁶, +0.03 · 10⁶, +0.03 · 10⁶, +0.10 · 10⁶, and +0.05 · 10⁶ mol s⁻¹, respectively, which result in a total southward inorganic carbon transport of only −0.06 · 10⁶ mol s⁻¹. An order of magnitude estimate of the meridional transport of dissolved organic carbon (DOC) has shown that in general this term cannot be ignored in the total carbon flux, this being +0.04 · 10⁶ to +0.16 · 10⁶ mol s⁻¹ at 58 °N. A simple carbon budget has been formulated for the temperate North Atlantic, using our flux estimates as well as those of Brewer et al. (1989). This budget shows that the divergence of the meridional carbon flux, connected with the freshwater balance of the ocean may be of the same order of magnitude as the divergence of the total inorganic carbon flux. For an accurate estimate of the total carbon budget of the ocean it will be necessary to take both the DOC transport and the effects of the freshwater balance into account.     

Nutrient flux in the Rhode River: Tidal transport of microorganisms in brackish marshes

Concentrations of bacteria, chlorophyll a, and several dissolved organic compounds were determined during 11 tidal cycles throughout the year in a high and a low elevation marsh of a brackish tidal estuary. Mean bacterial concentrations were slightly higher in flooding (7·1 × 10⁶ cells ml⁻¹) than in ebbing waters (6·5 × 10⁶ cells ml⁻¹), and there were no differences between marshes. Mean chlorophyll a concentrations were 36·7 μg l⁻¹ in the low marsh and 20·4 μg l⁻¹ in the high marsh. Flux calculations, based on tidal records and measured concentrations, suggested a small net import of bacterial and algal biomass into both marshes. Over the course of individual tidal cycles, concentrations of all parameters were variable and not related to tidal stage. Heterotrophic activity measured by the uptake of ³H-thymidine, was found predominantly in the smallest particle size fractions (< 1·0 μm). Thymidine uptake was correlated with temperature (r = 0·48, P < 0·01), and bacterial productivity was estimated to be 7 to 42 μg Cl⁻¹ day⁻¹.     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

Transport Through the Contraction Area in the Little Belt

The Great Belt, the Øresund and the Little Belt connect the central Baltic Sea and the Kattegat. A fixed station was moored in the contraction area in the Little Belt during the period 18–28 July 1995, measuring temperature, salinity and current in two levels, while discharge was measured by the RVDana. The composite Froude number calculated at the fixed station shows that the two layer flow through this area was most often supercritical. The discharges were satisfactorily related to the currents measured at the fixed station, and time-series of transports through the Little Belt were established. When compared to the transports through the Øresund the water transport ratio (Øresund:Little Belt) was found to be 4·4, while the salt transport ratio was found to be 3·0. The resistance of the Little Belt, when considering the differences in sea level from Gedser to Hornbæk, was 1839×10⁻¹² s² m⁻⁵. On the basis of water level and surface salinity measurements made during the period 1931–76, a net discharge of 2300 m³ s⁻¹and a net salt transport of 36 tonnes s⁻¹through the Little Belt from the central Baltic Sea were found.     

Direct measurements of diapycnal mixing in a fjord reach—Puget Sound's Main Basin

In the spring of 1988, time series of microstructure and ADCP current profiles were collected at four locations in the North Main Basin of Puget Sound, Washington. Depth and time averages of diapycnal diffusivity at the four stations (1.8−67.0×10⁻⁴ m² s⁻¹) were one to three decades above typical open-ocean thermocline levels. The buoyancy frequency-squared N² was near open-ocean levels, but unlike the open-ocean where N²S², finescale shear-squared S² was three to six times N² over significant portions of the water column at two of the stations. The time and space mean of all measurements ( ) is close to inferred vertical eddy diffusivity from a primitive equation model for Puget Sound (K_z=3×10⁻³ m² s⁻¹) (J. Geophys. Res. 96 (1991) 16779). Large time and space variability of K_ρ was found, with differences of inter-station, depth–time means over one decade. A simple scaling argument using the observed K_ρ suggests significant exchange of mass between the layers of the subtidal flow over the basin's residence time. Additionally, measurements show that local mixing may be comparable to volume-weighted sill mixing in modifying the Main Basin's stratification. Both are contrary to the “advective reach” simplification of fjord dynamics. The mixing levels were dominated by the passage of a mid-depth, southward-flowing density intrusion and what we interpret as a strongly advected, non-linear internal tide. These mechanisms elevated profile-averaged K_ρ by more than 10 times background levels, with sustained patches of K_ρ≥1×10⁻² m² s⁻¹. Critical 8-m gradient Richardson numbers (Ri₈<0.25) matching regions of overturns (>20 m) and strong turbulence suggest that shear instabilities dominated the turbulence production, though there was support for double-diffusive convection in the warm core of the density intrusion.     

Remineralization and accumulation of organic carbon and nitrogen in marine sediments of eutrophic bays: the case of the Bay of Concepcion, Chile

The Bay of Concepcion (36°40′S; 73°02′W) is a semi-enclosed and shallow embayment in which biogeochemical processes are seasonally coupled to coastal upwelling during the austral spring and summer. The nutrient cycle in the bay is complex due to the combined effects of a pronounced O₂ minimum layer and high nutrient concentrations both originating from subsurface equatorial water during coastal upwelling and a rapid rate of sediment nutrient recycling. The sediments are characterized by a high content of organic matter mainly due to the extremely high rates of phytoplankton production and deposition. During the upwelling period, a black flocculent layer frequently covers the sediment–water interface in the inner part of the bay where an extensive mat of Beggiatoa spp. develops. Three approaches are used to analyse the extent to which the benthic system recycles or retains nutrients at two stations, located at the centre (station C, St. C) and mouth (station B, St. B) of the bay for a 1-year period (March 1996–1997): (1) estimation of C and N remineralization rates based on SO₄²⁻ reduction measurements, (2) calculation of C and N turnover rates using a diagenetic model applied to total organic carbon and total nitrogen vertical distributions and, (3) construction of C and N budgets from direct measurements of sedimentation (from a sediment trap) and estimates of the C and N burial rates. Depth-integrated SO₄²⁻ reduction rates varied between 3.4 (winter) and 25.5 (summer) mmol m⁻² d⁻¹. Estimated C and N oxidation rates ranged between 7.9 and 87.8 mol C m⁻² yr⁻¹ and between 0.9 and 6.9 mol N m⁻² yr⁻¹, respectively. Each approach yielded minor differences in the C and N remineralization rates (and also minor differences between both studied stations), except when the kinetic model was applied to C and N distribution without including the presence of the flocculent layer. The rates of carbon oxidation and sulphate reduction were considerably higher than in other coastal sediments with similar depositional regime. The C and N burial rates were 2.23 and 0.21 (St. C) and 1.30 and 0.09 (St. B) mol m⁻² yr⁻¹, respectively. The C/N ratio of the buried fraction was ca. 10.6 at St. C and 14.4 at St. B. Because the observed differences in burial rates could not be ascribed to distinctive depositional (both stations have similar sediment accumulation rates) and oceanographic (similar O₂ concentration and hydrography) conditions, differences may be due to in part spatial heterogeneity in the supply of organic matter. The degree of preservation of organic matter as plankton detritus and nitrogen accumulating bacterial biomass associated with Beggiatoa spp. at St. C may also be involved.