Seasonal dynamics of inorganic nutrients and phytoplankton biomass in the NW Alboran Sea

The seasonal dynamics of inorganic nutrients and phytoplankton biomass (chlorophyll a), and its relation with hydrological features, was studied in the NW Alboran Sea during four cruises conducted in February, April, July and October 2002. In the upper layers, the seasonal pattern of nutrient concentrations and their molar ratios (N:Si:P) was greatly influenced by hydrological conditions. The higher nutrient concentrations were observed during the spring cruise (2.54 μM NO₃⁻, 0.21 μM PO₄³⁻ and 1.55 μM Si(OH)₄, on average), coinciding with the increase of salinity due to upwelling induced by westerlies. The lowest nutrient concentrations were observed during summer (<0.54 μM NO₃⁻, 0.13 μM PO₄³⁻ and 0.75 μM Si(OH)₄, on average), when the lower salinities were detected. Nutrient molar ratios (N:Si:P) followed the same seasonal pattern as nutrient distribution. During all the cruises, the ratio N:P in the top 20 m was lower than 16:1, indicating a NO₃⁻ deficiency relative to PO₄³⁻. The N:P ratio increased with depth, reaching values higher than 16:1 in the deeper layers (200–300 m). The N:Si ratio in the top 20 m was lower than 1:1, excepting during spring when N:Si ratios higher than 1:1 were observed in some stations due to the upwelling event. The N:Si ratio increased with depth, showing a maximum at 50–100 m (>1.5:1), which indicates a shift towards Si-deficiency in these layers. The Si:P ratio was much lower than 16:1 throughout the water column during the four cruises. In general, the spatial and seasonal variation of phytoplankton biomass showed a strong coupling with hydrological and chemical fields. The higher chlorophyll a concentrations at the depth of the chlorophyll maximum were found in April (2.57 mg m⁻³ on average), while the lowest phytoplankton biomass corresponded to the winter cruise (0.74 mg m⁻³ on average). The low nitrate concentrations together with the low N:P ratios found in the upper layers (top 20 m) during the winter, summer and autumn cruises suggest that N-limitation could occur in these layers during great part of the year. However, N-limitation during the spring cruise was temporally overcome by nutrient enrichment caused by an intense wind-driven upwelling event.     

Nitrogen uptake kinetics in the Ross Sea, Antarctica

The first estimates of uptake kinetic parameters for NH₄⁺, NO₃⁻, and urea in the Ross Sea, Antarctica were measured on three cruises during austral late winter–early spring 1996 (pre-bloom), late spring 1997 (bloom development), and summer 1997 (bloom decline). Nitrogen (N) uptake experiments were conducted with water collected at the 50% light penetration depth using trace-metal clean protocols and ¹⁵N tracer techniques. At all sites, ambient NO₃⁻ concentrations ranged from 5.8 to 30.5 μg-at N l⁻¹ and silicic acid concentrations were greater than 62.0 μg-at Si l⁻¹. The following trends were observed. First, based on maximum uptake rates (V_max), apparent N utilization followed the order NO₃⁻>NH₄⁺>urea during the pre-bloom and bloom development cruises. During the summer cruise, as the bloom was declining, the apparent order of utilization was NH₄⁺>NO₃⁻>urea. Second, evidence for possible repression of NO₃⁻ uptake by elevated NH₄⁺ concentrations was only observed at one site. Third, the kinetic parameters of NH₄⁺ uptake rates corrected for isotope dilution were compared with the kinetic parameters determined from uncorrected rates. In this comparison, the measure of substrate affinity, α (α=V_max/K_s) increased by an average of 4.6-fold when rates were corrected for isotope dilution, but values of V_max remained unchanged. Fourth, using bacterial production data, the magnitude of bacterial N uptake was estimated. Assuming that all bacterial N demands were met with NH₄⁺, the estimated bacterial portion of NH₄⁺ uptake ranged from <1%, when the ratio of bacteria to autotrophic biomass was low, to 35%, when bacterial abundance and biomass were highest. Finally, dramatic changes in NH₄⁺ uptake capacity were observed at one station (Stn. O), where kinetic parameters were measured during all three cruises. We hypothesize that a mutualistic relationship exists between phytoplankton and heterotrophic bacteria, and that the creation of microzones of high NH₄⁺ concentrations contributed to the changes seen at this station.     

Equilibrium and structural studies of silicon(IV) and aluminium(III) in aqueous solution. II. Formation constants for the monosilicate ions SiO(OH)3 and SiO2(OH)2. A precision study at 25°C in a simplified seawater medium

The hydrolysis of silicic acid, Si(OH)₄, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH⁻ was generated coulometrically. The total concentration of Si(OH)₄, B, and log[H⁺] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H⁺] 11.7, respectively. Within these ranges the formation of SiO(OH)₃⁻ and SiO₂(OH)₂²⁻ with formation constants log β₋₁₁(Si(OH)₄ SiO(OH)₃⁻ + H⁺) = −9.472 ±0.002 and log β₋₂₁(Si(OH)₄ SiO₂(OH)₂²⁻ + 2H⁺) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H⁺] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID.     

Short-term variability of fCO2 in seawater and air–sea CO2 fluxes in a coastal upwelling system (Ría de Vigo, NW Spain)

Coastal upwelling systems are regions with highly variable physical processes and very high rates of primary production and very little is known about the effect of these factors on the short-term variations of CO₂ fugacity in seawater (fCO₂^w). This paper presents the effect of short-term variability (<1 week) of upwelling–downwelling events on CO₂ fugacity in seawater (fCO₂^w), oxygen, temperature and salinity fields in the Ría de Vigo (a coastal upwelling ecosystem). The magnitude of fCO₂^w values is physically and biologically modulated and ranges from 285 μatm in July to 615 μatm in October. There is a sharp gradient in fCO₂^w between the inner and the outer zone of the Ría during almost all the sampling dates, with a landward increase in fCO₂^w.CO₂ fluxes calculated from local wind speed and air–sea fCO₂ differences indicate that the inner zone is a sink for atmospheric CO₂ in December only (−0.30 mmol m⁻² day⁻¹). The middle zone absorbs CO₂ in December and July (−0.05 and −0.27 mmol·m⁻² day⁻¹, respectively). The oceanic zone only emits CO₂ in October (0.36 mmol·m⁻² day⁻¹) and absorbs at the highest rate in December (−1.53 mmol·m⁻² day⁻¹).     

Seasonal methyltin and (3-dimethylsulphonio)propionate concentrations in leaf tissue of Spartina alterniflora of the Great Bay estuary (NH)

Concentrations of total recoverable inorganic tin (TRISn), monomethyltin (MeSn³⁺), dimethyltin (Me₂Sn²⁺), trimethyltin (Me₃Sn⁺) and (3-dimethylsulphonio)propionate (DMSP) were determined in leaves of Spartina alterniflora from three sites in the Great Bay estuary (NH) from 8 May to 15 September 1989. Total methyltin concentration increased from 8·9 ng g⁻¹ (fresh weight) on 8 May to 472 ng g⁻¹ on 23 May, decreased to 52 ng g⁻¹ on 7 June and 16ng g⁻¹ on 20 June, and remained low until the last sample on 18 September. Statistical calculations showed that methyltin concentrations varied significantly with sampling week, but not with site. DMSP concentrations showed very different behaviour. During the same sampling period DMSP concentrations varied only from 7·5 to 26 μmol g⁻¹ (fresh weight). DMSP concentrations varied significantly for site, but not sampling week.     

Investigation of the morphology of pore space in mudstones—first results

A suite of selected Tertiary mudstones was studied to improve the knowledge about microstructure and related transport processes in mudstones. Samples were investigated by mercury- and Wood's metal injection, SEM, XRD, and grain size analysis. Wood's metal injection has the advantage of visualising the ‘frozen’ injection process. The smallest pore casts observed were down to 40 nm in diameter, while the largest, bottle-shaped pores were up to 5 μm in diameter. Bottle-shaped pores occurred in all the samples, usually around silt or sand grains. One sample, which had a porosity of 28.5% according to mercury injection data, had not been impregnated by the molten alloy. We suggest this to reflect a strong deformation of the clay fabric by the high pressure without intrusion into the matrix. This raises questions about the reliability of mercury injection data for very fine-grained, highly porous sediments.After excluding these very fine-grained samples and one very calcareous sample regressions were found which relate porosity (φ), clay content (C), and sand content (S) to capillary displacement pressure (P_d(Hg)): P_d(Hg)=−25.05+0.63 C+0.29S (R²=0.92), and P_d(Hg)=−10.24+0.47 C−0.15φ (R²=0.88).     

Modelling of natural and synthetic polyelectrolyte interactions in natural waters by using SIT, Pitzer and Ion Pairing approaches

In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et₄NI and NaCl (for fulvic acid 0.1 < I /mol L^− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na⁺, K⁺, Mg²⁺, Ca²⁺) and anions (Cl⁻, SO₄²⁻) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments.     

Interactions of cadmium(II) and protons with dead biomass of marine algae Fucus sp.

Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol^− 1 min^− 1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g^− 1 (90 mg g^− 1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5.Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO₃ were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g^− 1, with median values of the affinity distribution for protons and cadmium ions, log K˜_H and log K˜_Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model.The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment.     

Alkalinity titration in seawater: How accurately can the data be fitted by an equilibrium model?

Displaying “calculated minus observed” data for precise titrations of seawater with strong acid permits direct evaluation of important parameters and detection of systematic errors.At least two data sets from the GEOSECS (Geochemical Ocean Sections) program fit an equilibrium model (which includes carbonate, borate, sulfate, silicate, fluoride, and phosphate) within the most stringent experimental error, less than 2 μmol kg⁻¹. The effect of various parameters on the fit of calculated to observed values depends strongly on pH. Although standard potential E₀, total alkalinity A_t, total carbonate C_t, and first acidity constant of carbon dioxide pK₁ are nearly independent, and can be determined for each data set, other parameters are strongly correlated. Within such groups, all but one parameter must be determined from data other than the titration curve.Adding an acid-base pair to the theoretical model (e.g. C_x=20 μmol kg⁻¹, pK_x=6.2) produces a deviation approaching 20 μmol kg⁻¹ at constant C_t; however, adjustment of C_t by about −18 μmol kg⁻¹ to produce a good fit leaves only ± 1.5 μmol kg⁻¹ residual deviation from the reference values. Thus, at current standards of precision, an unidentified weak acid cannot be distinguished from carbonate purely on the basis of the titration curve shape.There are few full sets of numerical data published, and most show larger systematic errors (3–12 μmol l⁻¹) than the above; one well-defined source is experiments performed in unsealed vessels. Total carbonate can be explicitly obtained as a function of pH by a rearrangement of the titration curve equation; this can reveal a systematic decrease in C_t in the pH range 5–6, as a result of CO₂ gas loss from the titration vessel. Attempts to compensate for this by adjustment of A_t, C_t, or pK₁ produce deviations which mimic those produced by an additional acid-base pair.Changing from the free H⁺ scale (for which [HSO₄⁻] and [HF] are explicit terms in the alkalinity) to the seawater scale (SWS) (where those terms are part of a constant factor multiplying [H⁺]) requires modification of the titration curve equation as well as adjustment of acidity constants. Even with this change, however, omission of pH-dependent terms in [HSO₄⁻] and [HF] produces small systematic errors at low pH.Shifts in liquid junction potential also introduce small systematic errors, but are significant only at pH <3. High-pH errors due to response of the glass electrode to Na⁺ as well as H⁺ can be adequately compensated to pH 9.5 by a linear selectivity expression.     

Ventilation of the North Pacific subtropical pycnocline and mode water formation

The annual subduction rate of the North Pacific was calculated based on isopycnally averaged hydrographic climatology (HydroBase), high-resolution winter mixed-layer climatology (NWMLC), and various wind stress climatologies from ship reports, numerical weather prediction products, and satellite products. The calculation was performed using Lagrangian coordinates in the same manner as in previous works, except a less smoothed oceanic climatology (HydroBase and NWMLC) was used instead of a World Ocean Atlas. Differences in the wind stress climatologies have very little effect on subduction rate estimates. The subduction rate census for density classes showed peaks corresponding to subtropical mode water (STMW), central mode water (CMW), and eastern subtropical mode water (ESTMW). The deeper mixed layer and the associated sharper mixed-layer fronts in the present climatology resulted in a larger lateral induction, which boosted the subduction rate, especially for the potential density anomaly (σ_θ) range of the lighter STMW (25.0 < σ_θ < 25.2 kg m⁻³) and lighter CMW (26.0 < σ_θ < 26.2 kg m⁻³), compared to previous estimates. The renewal time of permanent pycnocline water was estimated as the volume of water divided by the subduction rate for each σ_θ class: 2–4 years for ESTMW (24.5 < σ_θ < 25.2 kg m⁻³), 2 years for the lighter STMW (25.0 < σ_θ < 25.3 kg m⁻³), 5–9 years for the denser STMW (25.3 < σ_θ < 25.6 kg m⁻³), 10–20 years for the lighter CMW (26.0 < σ_θ < 26.2 kg m⁻³), 20–30 years for the middle CMW (26.2 < σ_θ < 26.3 kg m⁻³), and 60 years or longer for the denser CMW (26.3 < σ_θ < 26.6 kg m⁻³). A comparison of the water volume and subduction rate in potential temperature–salinity (θ–S) space indicated that the upper permanent pycnocline water (25.0 < σ_θ < 26.2 kg m⁻³) was directly maintained by nondiffusive subduction of winter surface water, including STMW and lighter CMW. The lower permanent pycnocline water (26.2 < σ_θ < 26.6 kg m⁻³) may be maintained through the subduction of fresher and colder water from the subarctic–subtropical transition region and subsequent mixing with saltier and warmer water. Diagnosis of the potential vorticity (PV) of the subducted water demonstrated that the low PV of STMW was mainly due to the large subduction rate, whereas that of both ESTMW and CMW was due mainly to the small density advection rate (cross-isopycnal flow). Additionally, a relatively large subduction rate probably contributes to the low PV of part of the lighter CMW (ESTMW) formed in the region around 38°N and 170°W (28°N and 145°W), which is characterized by a relatively thick winter mixed layer and an associated mixed-layer front, causing a large lateral induction rate.     

Cadmium, copper, lead and zinc in three species of planktonic crustaceans from the east coast of Corsica

Results of trace metal analyses performed on two species of Euphausiacea, Meganyctiphanes norvegica and Stylocheiron longicorne, and one species of Decapoda, Sergestes arcticus, collected off the east coast of Corsica, are reported. Analyses were carried out by atomic absorption spectrophotometry and by differential pulse anodic stripping voltammetry.S. arcticus contained lower concentrations of phosphorus (which was also analysed as a biological indicator), cadmium (0.33 μg g⁻¹), copper (17.7 μg g⁻¹), lead (2.13 μg g⁻¹) and zinc (51 μg g⁻¹) than the two Euphausiacea (0.50 μg Cd g⁻¹, 25.4 μg Cu g⁻¹, 4.03 μg Pb g⁻¹ and 59 μg Zn g⁻¹). Moreover, manganese concentrations were low in all the samples.When the results presented here are compared with previous results on phytoplankton and mesozooplankton, there appears to be no trend of trace metal enrichment from phytoplankton to the Decapoda.     

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).     

The speciation of Fe(II) and Fe(III) in natural waters

The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na⁺, Mg²⁺, Ca²⁺, K⁺, Sr²⁺, Cl⁻, SO₄⁻, HCO₃⁻, Br⁻, CO₃²⁻, B(OH)₄⁻, B(OH)₃ and CO₂) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl⁻, SO₄²⁻, OH⁻, HCO₃⁻, CO₃²⁻ and HS⁻) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (K_FeX^*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (K_FeX) and the activity coefficient of iron complexes (γ_FeX) with a number of inorganic ligands in NaClO₄ medium at various ionic strengths: In(K_FeX/γ_Feγ_X) = InK_FeX − In(γ_FeX) The activity coefficients for free ions (γ_Fe, γ_x) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (B_FeX, B_FeX⁰, C_FeX^φ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%.     

Nitrogen dynamics within a wind-driven eddy

Wind-driven cyclonic eddies are hypothesized to relieve nutrient stress and enhance primary production by the upward displacement of nutrient-rich deep waters into the euphotic zone. In this study, we measured nitrate (NO₃⁻), particulate carbon (PC), particulate nitrogen (PN), their stable isotope compositions (δ¹⁵N-NO₃⁻, δ¹³C-PC and δ¹⁵N-PN, respectively), and dissolved organic nitrogen (DON) within Cyclone Opal, a mature wind-driven eddy generated in the lee of the Hawaiian Islands. Sampling occurred in March 2005 as part of the multi-disciplinary E-Flux study, approximately 4–6 weeks after eddy formation. Integrated NO₃⁻ concentrations above 110 m were 4.8 times greater inside the eddy (85.8±6.4 mmol N m⁻²) compared to the surrounding water column (17.8±7.8 mmol N m⁻²). Using N-isotope derived estimates of NO₃⁻ assimilation, we estimated that 213±59 mmol m⁻² of NO₃⁻ was initially injected into the upper 110 m Cyclone Opal formation, implying that NO₃⁻ was assimilated at a rate of 3.75±0.5 mmol N m⁻² d⁻¹. This injected NO₃⁻ supported 68±19% and 66±9% of the phytoplankton N demand and export production, respectively. N isotope data suggest that 32±6% of the initial NO₃⁻ remained unassimilated. Self-shading, inefficiency in the transfer of N from dissolved to particulate export, or depletion of a specific nutrient other than N may have led to a lack of complete NO₃⁻ assimilation. Using a salt budget approach, we estimate that dissolved organic nitrogen (DON) concentrations increased from eddy formation (3.8±0.4 mmol N m⁻²) to the time of sampling (4.0±0.09 mmol N m⁻²), implying that DON accumulated at rate of 0.83±1.3 mmol N m⁻² d⁻¹, and accounted for 22±15% of the injected NO₃⁻. Interestingly, no significant increase in suspended PN and PC, or export production was observed inside Cyclone Opal relative to the surrounding water column. A simple N budget shows that if 22±15% of the injected NO₃⁻ was shunted into the DON pool, and 32±6% is unassimilated, then 46±16% of the injected NO₃⁻ remains undocumented. Alternative loss processes within the eddy include lateral exchange of injected NO₃⁻ along isopycnal surfaces, remineralization of PN at depth, as well as microzooplankton grazing. A 9-day time series within Cyclone Opal revealed a temporal depletion in δ¹⁵N-PN, implying a rapid change in the N source. A change in NO₃⁻ assimilation, or a shift from NO₃⁻ fueled growth to assimilation of a ¹⁵N-deplete N source, may be responsible for such observations.     

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.     

Nutrients (organic C, P, N, Si) in the eutrophic River Loire (France) and its estuary

The Loire estuary has been surveyed from 1982 to 1985 by 13 isochronous longitudinal profiles realized at low tide. Nutrient (SiO₂, NO₃⁻, NH₄⁺, PO³⁻₄, particulate organic carbon or POC) patterns are very variable depending on the season, the estuarine section [river, upper-inner estuary, upstream of the fresh-water-saline-water interphase FSI, the lower-inner estuary characterized by the high turbidity zone (HTZ), the outer estuary] and the river discharge. Biological processes are dominant. In the eutrophied River Loire (summer pigment > 100 μg l⁻¹), the high algal productivity (algal POC > 3 mg l⁻¹) results in severe depletion of SiO₂, PO₄³⁻, NO₃⁻. The enormous biomass (55 000 ton algal POC/year) is degraded in the HTZ where bacterial activity is intense. As a result, there is generally a regeneration of dissolved SiO₂ and PO₄³⁻, a marked NH₄⁺ maximum, while NO₃⁻ is conservative or depleted when the HTZ is nearly anoxic. Other processes can be considered including pollution from fertilizer plans (PO₄³⁻, NH₄⁺) and from a hydrothermal power plant (NH₄⁺). In the less turbid outer estuary, nutrients are generally conservative. Major variations of concentrations are observed in the lowest chlorinity section (Cl⁻ < 1 g kg⁻) and also upstream the FSI, defined here as a 100% increase in Cl⁻. Nutrient inputs to the ocean are not significantly modified for SiO₂ and NO₂⁻, but are increased by 70% and 180% for PO₄³⁻ and NH₄⁺ and depleted by 60% for POC. Odd hydrological events, especially some floods, may perturbate or even mask the usual seasonal pattern observed in profiles.     

Microscale gradients of planktonic microbial communities above the sediment surface in a mangrove estuary

The microscale (1 and 4 cm sampling resolution) distributions of chemical (O₂, NH₃, NO₃⁻, NO₂⁻, PO₄³⁻) and biological (Chl a, phytoplankton, bacterioplankton, viruses) parameters were measured in the 16 cm of water immediately overlaying the sediment-water interface (SWI) within a temperate mangrove estuary in South Australia during December 2003 and March 2004. Shear velocities (u_*) during the time of sampling were very low (<0.1 cm s⁻¹), and we consequently predict that resuspension of organisms and materials was negligible. In December 2003, profiles were often characterised by strong gradients in nutrients and organisms, with the highest concentrations often observed within 0.5 cm of the SWI. Microscale patterns in O₂, NH₃, NO₃⁻ and NO₂⁻ indicated that a variety of anaerobic and aerobic transformation processes probably occurred at the SWI and within profiles. Strong gradients in PO₄³⁻ were indicative of nutrient flux across the SWI as a consequence of degradation processes in the sediments. Pico- and nanophytoplankton concentrations were strongly correlated (p < 0.01) to PO₄³⁻, and exhibited 12- and 68-fold changes in abundance, respectively, with highest concentrations observed nearest to the SWI. Several bacterial subpopulations were discriminated using flow cytometry and significant shifts in the ‘cytometric structure’ of the bacterial community were observed within microscale profiles. Two populations of viruses were correlated to the phytoplankton and low DNA (LDNA) bacteria, and each exhibited elevated concentrations within 0.5 cm of the SWI. In March 2004, microscale distributions of O₂ and nutrients were more homogenous than in December 2003, and dissimilar microbial community structure and patterns were observed above the SWI. The patterns observed here support the prediction that benthic processes can strongly influence the ecology of planktonic communities in the overlaying water, and provide further evidence for the existence of microscale variability amongst communities of aquatic microorganisms.     

Effects of nitrogen and iron enrichments on phytoplankton communities in the Northwestern Indian Ocean

Nutrient-enrichment bottle experiments in the northwestern Indian Ocean surface waters were conducted to investigate phytoplankton growth following enrichments with either NH₄⁺, NO₃⁻, Fe or Fe + NO₃⁻. Stimulation of phytoplankton growth could be achieved by the addition of either NH₄⁺ or NO₃⁻ under the ambient Fe concentrations, but the most significant increases in Chl a, POC, and cell densities were observed in the Fe + NO₃⁻-amended culture. Iron addition caused more rapid responses of phytoplankton growth in the Fe + NO₃⁻ treatment than those in the NO₃⁻ and NH₄⁻ treatment. However, the Fe-enrichment treatment revealed minimal growth of phytoplankton because of severe major nutrient deficiency and was similar to the control treatment. Increases in the cell density of diatoms and spherical phytoplankton cells (< 10 μm) were significant in the NH₄⁺-enriched samples, whereas NO₃⁻ enrichment alone had little effect on the diatoms. Simultaneous addition of Fe and NO₃⁻ stimulated maximal growth of phytoplankton, in particular in diatoms, coccolithophorids and Phaeocystis type colonies. However, the dominance of coccolithophorids and Phaeocystis type colonies in the Fe + NO₃⁻ treatment may be interpreted as resulting from Si-limitation. The high N/P ratio for phytoplankton nutrient uptake in the N-amended culture indicates the possibility of some P-limited growth. From these results, we conclude that in the northwestern Indian Ocean, Fe and major nutrients are co-limiting phytoplankton production during the northeast monsoon. Iron appeared to affect the ability of phytoplankton to respond quickly to transient nutrient inputs.     

Benthic fluxes of nitrogen in the tidal reaches of a turbid, high-nitrate sub-tropical river

Benthic fluxes of dissolved inorganic nitrogen (NO₃⁻ and NH₄⁺), dissolved organic nitrogen (DON), N₂ (denitrification), O₂ and TCO₂ were measured in the tidal reaches of the Bremer River, south east Queensland, Australia. Measurements were made at three sites during summer and winter. Fluxes of NO₃⁻ were generally directed into the sediments at rates of up to −225 μmol N m⁻² h⁻¹. NH₄⁺ was mostly taken up by the sediments at rates of up to −52 μmol N m⁻² h⁻¹, its ultimate fate probably being denitrification. DON fluxes were not significant during winter. During summer, fluxes of DON were observed both into (−105 μmol m⁻² h⁻¹) and out of (39 μmol m⁻² h⁻¹) the sediments. Average N₂ fluxes at all sampling sites were similar during summer (162 μmol N m⁻² h⁻¹) and winter (153 μmol N m⁻² h⁻¹). Denitrification was fed both by nitrification within the sediment and NO₃⁻ from the water column. Sediment respiration rates played an important role in the dynamics of nitrification and denitrification. NO₃⁻ fluxes were significantly related to TCO₂ fluxes (p<0.01), with a release of NO₃⁻ from the sediment only occurring at respiration rates below 1000 μmol C m⁻² h⁻¹. Rates of denitrification increased with respiration up to TCO₂ fluxes of 1000 μmol C m⁻² h⁻¹. At sediment respiration rates above 1000 μmol C m⁻² h⁻¹, denitrification rates increased less rapidly with respiration in winter and declined during summer. On a monthly basis denitrification removed about 9% of the total nitrogen and 16% of NO₃⁻ entering the Bremer River system from known point sources. This is a similar magnitude to that estimated in other tidal river systems and estuaries receiving similar nitrogen loads. During flood events the amount of NO₃⁻ denitrified dropped to about 6% of the total river NO₃⁻ load.     

Chromium(VI) reduction by sulphur(IV) in aqueous solutions

The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔH_app of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression

−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]²