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.     

Iron availability and the release of iron-complexing ligands by Emiliania huxleyi

The ubiquitous algal species, Emiliania huxleyi, was incubated in sea water supplemented only with nitrate and phosphate (N and P) without chelating agents to control metal speciation. Growth was slow in a “low-iron” culture containing 1.3 nM iron and was found to be iron-limited, growth-accelerating when a 1-nM iron addition was made. The growth rate in a “high-iron” culture (5.4 nM iron) was greater, reaching 0.4 div day⁻¹ but this culture too was found to have become iron-limited when a 9-nM iron addition was made on day 17 of the incubation. Both cultures were found to release iron-complexing ligands in excess of the iron concentration, 6 nM in the low-iron culture, and 10 nM in the high-iron culture. More ligands were produced after the iron addition taking the ligand concentration to 11 nM in the low-iron culture. The data show that the ligands are released in response to the iron addition, when at least some of the iron had already been taken up. This type of release is contrary to the concept of a siderophore, which is supposed to be released in periods of lack of iron; however the increase in the ligand concentration is similar to that released by the natural community in response to the iron addition in the IRON-EX II experiment [Rue, E.L., Bruland, K.W., 1997. The role of organic complexation on ambient iron chemistry in the equatorial Pacific Ocean and the response of a mesoscale iron addition experiment. Limnol. Oceanogr. 42, 901–910]. The enhanced growth in the cultures when more iron was added indicated that the organically complexed iron present in the cultures was not immediately available to the organisms (or at least not at sufficiently high rate), and that the organisms responded to freshly added, inorganic, iron.     

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.     

Surface boundary-layer variability off Northern California, USA, during upwelling

A five-element mooring array is used to study surface boundary-layer transport over the Northern California shelf from May to August 2001. In this region, upwelling favorable winds increase in strength offshore, leading to a strong positive wind stress curl. We examine the cross-shelf variation in surface Ekman transport calculated from the wind stress and the actual surface boundary-layer transport estimated from oceanic observations. The two quantities are highly correlated with a regression slope near one. Both the Ekman transport and surface boundary layer transport imply curl-driven upwelling rates of about 3×10⁻⁴ m s⁻¹ between the 40 and 90 m isobaths (1.5 and 11.0 km from the coast, respectively) and curl-driven upwelling rates about 1.5×10⁻⁴m s⁻¹ between the 90 and 130 m isobaths (11.0 and 28.4 km from the coast, respectively). Thus curl-driven upwelling extends to at least 25 km from the coast. In contrast, upwelling driven by the adjustment to the coastal boundary condition occurs primarily inshore of the 40-m isobath. The upwelling rates implied by the differentiating the 40-m transport observations with the coastal boundary condition are up to 8×10⁻⁴ m s⁻¹. The estimated upwelling rates and the temperature–nitrate relationship imply curl-driven vertical nitrate flux divergences are about half of those driven by coastal boundary upwelling.     

On the relevance of iron adsorption to container materials in small-volume experiments on iron marine chemistry: Fe-aided assessment of capacity, affinity and kinetics

Iron chemistry in seawater has been extensively studied in the laboratory, mostly in small-volume sample bottles. However, little has been reported about iron wall sorption in these bottles. In this paper, radio-iron ⁵⁵Fe was used to assess iron wall adsorption, both in terms of capacity, affinity and kinetics. Various bottle materials were tested. Iron sorption increased from polyethylene/polycarbonate to polymethylmetacrylate (PMMA)/high-density polyethylene/polytetrafluoroethylene to glass/quartz, reaching equilibrium in a 25–70 h period. PMMA was studied in more detail: ferric iron (Fe(III)) adsorbed on the walls of the bottles, whereas ferrous iron (Fe(II)) did not. Considering that in seawater the inorganic iron pool mostly consists of ferric iron, the wall will be a factor that needs to be considered in bottle experiments.The present data indicate that for PMMA with specific surface (S)-to-volume (V) ratio S/V, both iron capacity (42 ± 16 × 10^− 9 mol/m² or 1.7 × 10^− 9 mol/L recalculated for the S/V-specific PMMA bottles used) and affinity (log K_Fe'W = 11.0 ± 0.3 m²/mol or 12.4 ± 0.3 L/mol, recalculated for the S/V-specific PMMA bottles used) are of similar magnitude as the iron capacity and -affinity of the natural ligands in the presently used seawater and thus cannot be ignored.Calculation of rate constants for association and dissociation of both Fe'L (iron bound to natural occurring organic ligands) and Fe'W (iron adsorbed on the wall of vessels) suggests that the two iron complexes are also of rather similar kinetics, with rate constants for dissociation in the order of 10 ⁻⁴–10^− 5 L/s and rate constants for association in the order of 10⁸ L/(mol s). This makes that iron wall sorption should be seriously considered in small-volume experiments, both in assessments of shorter-term dynamics and in end-point observations in equilibrium conditions. Therefore, the present data strongly advocate making use of iron mass balances throughout in experiments in smaller volume set-ups on marine iron (bio) chemistry.     

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.     

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.     

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.     

Transformation dynamics and reactivity of dissolved and colloidal iron in coastal waters

We have investigated the chemical forms, reactivities and transformation kinetics of Fe(III) species present in coastal water with ion exchange and filtration methods. To simulate coastal water system, a mixture of ferric iron and fulvic acid was added to filtered seawater and incubated for a minute to a week. At each incubation time, the seawater sample was acidified with hydrochloric acid and then applied to anion exchange resin (AER) to separate negatively charged species (such as fulvic acid, its complexes with iron and iron oxyhydroxide coated with fulvic acid) from positively charged inorganic ferric iron (Fe(III)′). By monitoring the acid-induced Fe(III)′ over an hour, it was found that iron complexed by fulvic acid dissociated rapidly to a large extent (86–92% at pH 2), whereas amorphous ferric oxyhydroxide particles associated with fulvic acid (AFO-L) dissociated very slowly with the first-order dissociation rate constants ranging from 6.1 × 10^− 5 for pH 3 to 2.7 × 10^− 4 s^− 1 for pH 2. Therefore, a brief acidification followed by the AER treatment (acidification/AER method) was likely to be able to determine fulvic acid complexes and thus differentiate the complexes from the AFO-L particles (the dissolution of AFO-L was insignificant during the brief acidification). The acidification/AER method coupled with a simple filtration technique suggested that the iron–fulvic acid complexes exist in both the < 0.02 μm and 0.02–0.45 μm size fractions in our coastal water system. The truly dissolved iron (< 0.02 μm) was relatively long-lived with a life-time of 14 days, probably due to the complexation by strong ligands. Such an acid-labile iron may be an important source of bioavailable iron in coastal environments, as a significant relationship between the chemical lability and bioavailability of iron has been well recognised.     

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.     

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.     

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.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

Nitrogen cycling in the southern North Sea: consequences for total nitrogen transport

Nitrate and ammonium uptake rates were measured during a series of cruises in the well-mixed region of the southern North Sea from February to September. Water column-integrated uptake rates ranged between 0.01 and 8.7 mmol N m⁻² d⁻¹ and 0.01 and 12.2 mmol N m⁻² d⁻¹ for nitrate and ammonium, respectively, with ammonium uptake dominating after the phytoplankton spring bloom in May. A moored buoy continuously measuring nitrate and chlorophyll a and seabed current meters were also deployed in the central southern North Sea in the region of the East Anglian plume—a permanent physical feature which transports nutrients towards continental Europe. This enabled the flux of water and hence of nutrients across the southern North Sea to be determined and an assessment of the contribution of freshwater nutrients to the flux to be made. A simple box model is developed to relate the phytoplankton uptake of nitrate and ammonium to the transport of nitrate, ammonium and particulate organic matter (POM) across the southern North Sea. This showed the importance of the plume region of the North Sea in the processing of nitrogen, with nitrate dominating total nitrogen transport prior to the spring bloom (10 340×10³ kg N inflow to the plume in March) and transport of nitrogen as ammonium, nitrate and POM in approximately equivalent amounts during summer (2560, 2960 and 2151×10³ kg N inflow to the plume, respectively, in July). The box model also demonstrates more generally the need to assess nitrogen transport as nitrate, ammonium and POM if an improved understanding of the impact of nutrient input in shelf seas is to be achieved.     

Impact of environmental factors on in situ determination of iron in seawater by flow injection analysis

A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (C_p = 2.8 × 10^{− 5}P + 3.4 × 10^{− 2} s nmol^{− 1}, R² = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (C_Θ = 0.009e^0.103Θ, R² = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fe_a (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fe_a (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).     

A 1998–1992 comparison of inorganic carbon and its transport across 24.5°N in the Atlantic

In January and February 1998, when an unprecedented fourth repetition of the zonal hydrographic transect at 24.5°N in the Atlantic was undertaken, carbon measurements were obtained for the second time in less than a decade. The field of total carbon along this section is compared to that provided by 1992 cruise which followed a similar path (albeit in a different season). Consistent with the increase in atmospheric carbon levels, an increase in anthropogenic carbon concentrations of 8±3 μmolkg⁻¹ was found in the surface layers. Using an inverse analysis to determine estimates of absolute velocity, the flux of inorganic carbon across 24.5° is estimated to be −0.74±0.91 and −1.31±0.99 PgCyr⁻¹ southward in 1998 and 1992, respectively. Estimates of total inorganic carbon flux depend strongly upon the estimated mass transport, particularly of the Deep Western Boundary Current. The 1998 estimate reduces the large regional divergence in the meridional carbon transport suggested by previous studies and brings into question the idea that the tropical Atlantic constantly outgasses carbon, while the subpolar Atlantic sequesters it. Uncertainty in the carbon transports themselves, dominated by the uncertainty in the total mass transport estimates, are a hindrance to determining the “true” picture.The flux of anthropogenic carbon (C_ANTH) across the two transects is estimated as northward at 0.20±0.08 and 0.17±0.06 PgCyr⁻¹ for the 1998 and 1992 sections, respectively. The net transport of C_ANTH across 24.5°N is strongly affected by the difference in concentrations between the northward flowing shallow Florida Current and the mass balancing, interior return flow. The net northward transport of C_ANTH is opposite the net flow of total carbon and suggests, as has been found by others, that the pre-industrial southward transport of carbon within the Atlantic was stronger than it is today. Combining these flux results with estimates of atmospheric and riverine inorganic carbon input, it is determined that today's oceanic carbon system differs from the pre-industrial system in that today there is an uptake of anthropogenic carbon to the south that is advected northward and stored within the North Atlantic basin.     

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.     

Buoy measured wind, wind stress and wind stress curl over the shelf off Bodega Bay, California

An array of five buoys and three coastal stations is used to characterize the winds, stress, and curl of the wind stress over the shelf off Bodega Bay, California. The wind and wind stress are strong and persistent in the summer and weak in the winter. In the summer, wind and stress decrease strongly across the shelf, toward the coast. Combinations of buoys are used to compute the curl of the wind stress over different portions of the shelf. The mean summer 2001 curl of the wind stress over the array depends upon the area selected, varying between −1.32×10⁻⁶ and +7.80×10⁻⁶ Pa m⁻¹. The winter 2002 wind-stress curl also depends on location, varying from −2.06×10⁻⁶ to +2.78×10⁻⁶ Pa m⁻¹. Mean monthly curl of the wind stress is a maximum in the summer and a minimum near zero in the winter. In both the summer and the winter, the correlation between the wind-stress curl for different portions of the shelf varies between moderate negative, though insignificance, to high positive. A wind measurement at a single point can be poorly related to the measured curl of the wind stress at other locations over the shelf. The measurements show that the use of one wind measurement to characterize the curl of the wind stress over the shelf without further investigation of the local wind-stress curl structure is risky.     

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]].     

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.