Measurement of the redox speciation of iron in seawater by catalytic cathodic stripping voltammetry

Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (Fe_R) in the absence and presence of 2 μM Dp, Fe_R being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H₂O₂ and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for Fe_R. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for Fe_R, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of Fe_R ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column.     

Risk of dike failure due to flow slides

Flow slides may affect the stability of dikes. A flow slide is an instability of a submerged slope caused by liquefaction of loose, (medium) fine sand. Whether a flow slide will occur depends on the properties of the sand, which are a function of its density, and the geometry of the slope, as determined by wave and current induced scour and sedimentation. The influence of sand properties and the geometry parameters on the risk of flow slides are discussed. The application of a flow slide prediction method to an example and a risk analysis is briefly discussed.     

Transient biouptake flux and accumulation by microorganisms: The case of two types of sites with Langmuir adsorption

The uptake of a chemical species by an aquatic microorganism is modelled considering two kinds of sites where Langmuirian adsorption is followed by first order internalisation kinetics. Simpler models, such as only one internalisation route (while most of the adsorption takes place on non-internalising sites) or a linear isotherm for adsorption on one or both sites, become limiting cases of this double-Langmuirian model. The model considers the sites located on the spherical (or semi-spherical) surface of the organism, and takes diffusion from the medium into explicit account. The numerical solution for the internalisation flux shows a maximum. We provide an estimate for the time needed to reach a certain proximity to steady state. The transient solution confirms that the analytical expressions for the steady-state flux are usually valid and that the accumulated amounts reflect the impact of the short-time uptake. The Instantaneous Steady-State Approximation (ISSA), where an intercept of the linear regression of accumulated amount as a function of time is interpreted as an adsorbed amount, can be critically assessed with the transient numerical code for two cases: (i) when the total burden of metal on the cell is the input data and (ii) when an extraction procedure provides further information on the adsorbed and internalised amount.     

The expression of CYP1A,vitellogenin and zona radiata proteins in Atlantic salmon (Salmo salar) after oral dosing with two commercial PBDE flame retardant mixtures: absence of short-term responses

The short-term effects of the commercial PBDE flame retardant mixtures Penta-BDE and cta-BDE on the expression of cytochrome P450 1A (CYP1A), vitellogenin (Vtg) and zona radiata proteins (Zrp) were investigated in juvenile salmon (Salmo salar). For this purpose, groups of fish were dosed twice (oral intake at days I and 4) with 10 and 50 mg/kg body weight of both commercial mixtures. The fishes were sacrificed at day 7 (n = 5 for each group) and 14 (n = 6 for each group), and blood, liver, fillet, and brain were collected. Blanks and positive controls were also part of the experiment. The expressions of Vtg, Zrp, and CYPIA were measured with several techniques (EROD, ELISA, Western, Northern and Slot Blot). The values in the groups of fish treated with Penta-BDE or Octa-BDE did not significantly differ from the reference group for any of the parameters tested. In contrast, the positive control groups treated with estradiol-17beta for Vtg and Zrp expression, and beta-naphthoflavone for CYP1A expression did show a significant response, indicating the potential sensitivity of the fishes for the parameters measured. Since the results of the chemical analyses showed concentrations of a number of PBDE congeners in liver, fillet, and brain that were about three orders of magnitude above those of fish from the North Sea, it is concluded that the short-term toxicity of both commercial PBDE mixtures for these endpoints was low.     

The morphodynamic modelling of tidal sand waves on the shoreface

An artificial sand wave on the Dutch shoreface of the North Sea has been studied in conditions with relatively strong tidal currents in the range of 0.5 to 1 m/s and sediments in the medium sand size range of 0.2 to 0.5 mm. The sand wave is perpendicular to the tidal current and has a maximum height and length of the order of 5 m and 1 km, respectively. The sand wave is dynamically active and shows migration rates of the order of a few metres per year. A numerical morphodynamic model (DELFT3D model) has been used to simulate the morphological behaviour of the sand wave in the North Sea. This model approach is based on the numerical solution of the three-dimensional shallow water equations in combination with a surface wave propagation model (wind waves) and the advection–diffusion equation for the sediment particles with online bed updating after each time step. The model results show that the sand wave grows in the case of dominant bed-load transport (weak tidal currents; relatively coarse sediment; small roughness height; low waves) and that the sand wave decays in the case of dominant suspended transport (strong currents, relatively fine sediment, large roughness height; storm waves).     

Trace element fractionation and distribution in turbidites,homogeneous and pelagic deposits; the Zaire Fan,Southeast Atlantic Ocean

In turbidites, homogeneous and pelagic deposits of the Zaire Fan Th, La, Sm, and Rb and to a lesser extent Yb and Ta correlate strongly. La, Sm, Yb, Rb, Ta, and Th increase two-fold in Te3 turbidite intervals relative to Te 1 due to an increase in clay fraction with which these elements occur associated preferentially.Hf and Zr are anomalously high in Tel and Tel intervals which is probably a result of mineral separation. Zr is absent in Te3 intervals and the homogenous and pelagic deposits. Ba, Br. and U are lowest in turbidites and highest in homogenous continental slope deposits which is probably caused by upwelling. Cc anomalies may be related to the crystallinity of smectite.     

Stability analysis of a two-inlet bay system

The stability analysis for a double-inlet bay system is applied to an inlet system resembling Big Marco Pass and Capri Pass on the lower west coast of Florida. Since the opening of Capri Pass in 1967, the length of Big Marco Pass has increased from 2000 m in 1967 to 3000 m in 1988 and the cross-sectional area has decreased from 1200 m² in 1967 to 1000 m² in 1988. Since 1967, the cross-sectional area of Capri Pass has steadily increased and in 1988 was 700 m². Tides off the inlets are of the mixed type with a diurnal range of 1 m. The gross littoral transport rate in the vicinity of the inlets is estimated at 150,000 m³ yr⁻¹.For each inlet the maximum tidal velocities are calculated as a function of the gorge cross-sectional areas using a lumped-parameter model to describe the hydrodynamics of the flow. In the model it is assumed that the bay level fluctuates uniformly and the bay surface area remains constant. The velocities are used to calculate the tidal maximum of the bottom shear stress in each inlet as a function of the cross-sectional areas of the two inlets (=closure surface). Values of the equilibrium shear stress are derived from an empirical relationship between cross-sectional area and tidal prism for stable inlets along the west coast of Florida. Closure surfaces and equilibrium stress values are calculated for values of friction factors ranging from F=4×10⁻³ to F=6×10⁻³. Using the closure surfaces and equilibrium stress values, the equilibrium flow curve for each inlet is determined. The equilibrium flow curve represents the locus of the combination of cross-sectional areas for which the actual bottom shear stress in the inlet equals the equilibrium shear stress.Based on the equilibrium flow curves and the known values of the cross-sectional areas of the two inlets in 1988, it is expected that, ultimately, Big Marco Pass will close and Capri Pass will remain as the sole inlet with a cross-sectional area of 1250 m² and a maximum tidal velocity pertaining to a diurnal tide of 0.85 m s⁻¹.     

Diet shifts of Caribbean grunts (Haemulidae) and snappers (Lutjanidae) and the relation with nursery-to-coral reef migrations

The spatial size distribution of grunts and snappers have previously indicated the separation of juveniles in nursery habitats from the adults on the coral reef. This implies life cycle migrations from nursery habitats (such as seagrass beds and mangroves) to the coral reef. If diet shifts are related to such migrations, then the diets of these fish must change before or around the fish size at which such migrations take place. A wide size range of juveniles of two grunt species (Haemulon sciurus and Haemulon flavolineatum) and of two snapper species (Lutjanus apodus and Ocyurus chrysurus) were caught in seagrass beds and mangroves, and their gut contents identified and quantified. Regression analysis between fish size and dietary importance of small crustaceans showed a negative relationship in all four species. Positive relations were found for H. sciurus, L. apodus and O. chrysurus between fish length and the dietary importance of decapods, and for L. apodusand O. chrysurus between fish length and prey fish importance. Critical changes in the fish diets with fish size were examined by application of a Canonical Correspondence Analysis (CCA). The CCA yielded three clusters of size-classes of fishes with similar diets, and application of a Mantel test showed that each of these clusters had significantly different diets, and that each cluster diet was significantly specialised. The size at which a fish species ‘switched’ from one cluster to another was compared with size-at-maturity data and with the typical size at which these species migrate from the nursery habitats to the coral reef. H. sciurus and H. flavolineatum may be prompted to migrate from the nursery habitats to coral reef habitats because of dietary changes, or because of the development of the gonads. For L. apodus and O. chrysurus, a dietary changeover forms a more likely explanation for nursery-to-reef migrations than does sexual maturation because these species reach maturity at sizes much larger than the maximum size of individuals found in nursery habitats. Although other factors may theoretically initiate or promote the migration patterns, the results of this study indicate that ontogenetic dietary changes may crucially influence the nursery-to-coral reef migrations of these reef fish species.