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.     

Circulation

Low-frequency current and temperature variability on the southeast US continental shelf during summer conditions of weak wind forcing and vertical stratification was found to be similar in many aspects to previous findings for winter, when stronger wind forcing and vertical homogeneity prevails. Subtidal variability in the outer shelf is dominated by the weekly occurrence of Gulf Stream frontal eddies and meanders. These baroclinic events strongly affect the balance of momentum in the outer shelf, but not at mid-shelf. A negative alongshore sea level slope of order −10⁻⁷ is required to balance mean along-shelf momentum at the shelf edge, similar to oceanic estimates, and can contribute to the observed northward mean flow over the shelf.Low-frequency flow at mid-shelf and coastal sea level fluctuations appear to occur as a forced wave response to local alongshore wind stress events that are coherent over the shelf domain. Momentum balances indicate a trapped wave response similar to the arrested topographic wave found in the mid-Atlantic Bight (CSANADY, 1978). Density driven currents from river discharge do not appear to be significant at mid-shelf. Cold, subsurface intrusions of deeper, nutrient rich Gulf Stream waters can occasionally penetrate to mid- and inner-shelf regions north of Cape Canaveral, causing strong phytoplankton and zooplankton responses. These events were observed following the simultaneous occurrence of upwellings from northward winds and Gulf Stream frontal eddies at the shelf break during periods when the Stream was in an onshore position. Subsurface Gulf Stream intrusions to mid-shelf occur only during the summer, when the shelf is vertically stratified and cross-shelf density gradients do not present a barrier as in winter.     

On the sulphur chemistry of a super-anoxic fjord, Framvaren, South Norway

The concentrations of total carbonate (C_t), sulphate, sulphide, thiols and oxygen, the ratio between the stable sulphur isotopes ³⁴S and ³²S in sulphate and sulphide, and the density (used to calculate salinity) were determined on samples from the water column of Framvaren, a superanoxic fjord in southern Norway. From a depth of 18m (the oxic-anoxic boundary) the initial sulphate concentration, ([SO₄]_init), as calculated from salinity, is significantly higher than the sum of the measured sulphur species. This is attributed to a loss of sulphur from the water column. The amount of total carbonate produced, corrected for the initial concentration (C_t - 2.4 Sal/35) is found to be proportional to the amount of sulphate consumed, ([SO₄]_init - [SO₄]), according to the following relation C_t- 2.4 Sal/35 = 1.84 ([SO₄]_init - [SO₄]). Isotopic fractionation caused by bacterial sulphate reduction in the anoxic part of the water column produces sulphide with a δ³⁴S 40‰ lower than the δ³⁴S for sulphate at corresponding depths. The isotopic fractionation also results in δ³⁴S value for the remaining sulphate at depths below 80 m being considerably higher than the mean value for ocean water, which is close to + 20‰. The δ³⁴S values for sulphate at depths between 10 and 50 m were lower than + 20‰ which indicates oxidation of sulphide, which follows upon diffusion of sulphide from deeper parts of the water column and inflow of oxygenated seawater over the sill into the anoxic water of the fjord. A conclusive scenario of the Framvaren sulphur chemistry is presented.     

Robust Range-Only Beacon Localization

In this paper, we present a system capable of simultaneously estimating the position of an autonomous underwater vehicle (AUV) and the positions of stationary range-only beacons. Notably, our system does not require beacon positions a priori, and our system performs well even when range measurements are severely degraded by noise and outliers. We present a powerful outlier rejection method that can identify groups of range measurements that are consistent with each other, and a method for initializing beacon positions in an extended Kalman filter (EKF). We have successfully applied our algorithms to real-world data and have demonstrated a simultaneous localization and mapping (SLAM) system whose navigation performance is comparable to that of systems that assume known beacon locations     

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.     

Fractal Dimension and Fractals in Ocean Engineering

- This paper discusses the application of fractal dimension and fractals in ocean engineering. To handle some ocean environment problems, the existing fractal method, in which the fractal dimension is a constant, can be used. For some complicated problems in ocean engineering, this paper presents the concept of the variable dimension fractals (D = f(r)), i. e., the fractal dimension D is the function of characteristic scale r instead of a constant. By using variable dimension fractals, several deformation and stress states of offshore structures are described.     

A case study of a modified gravity type cage and mooring system using numerical and physical models

A modified gravity-type cage, developed by SADCO Shelf Ltd., was examined using numerical and physical models to determine if the cage and mooring system is suitable for an exposed site south of the Isles of Shoals, NH. The 3000-m/sup 3/ SADCO Shelf Submersible Fish Cage has angled stays between the upper framework and the ballasted bottom rim (in addition to net) to resist the horizontal shear deformation. The mooring system consists of three legs-each made up of a taut vertical chain and an angled rope, both leading to deadweight anchors. Normalized response amplitudes (response amplitude operators) were found for motion response in heave, surge and pitch, and load response in the anchor and bridle lines, in regular (single frequency) waves. In addition, a stochastic approach was taken to determine the motion and load transfer functions in random waves using a spectrum representative of seas at the selected site. In general, the system motion had a highly damped response, with no resonant peaks within the wave excitation range of 0.05 to 0.45 Hz. The anchor line force response was at all frequencies below 5 kN per meter of wave amplitude. The physical model tests showed consistently more conservative (larger) results compared to those for the numerical model.     

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.