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.     

Morphodynamics of a bar-trough surf zone

A field study was made of the distinguishing morphodynamic processes operating in a surf zone which perennially exhibits accentuated bar-trough topography (the “longshore-bar-trough” and “rhytmic-bar-and-beach” states as described by Wright and Short, 1984). Characteristic features of the morphology include a shallow bar with a steep shoreward face, a deep trough, and a steep beach face. This morphology, which is favored by moderate breaker heights and small tidal ranges, strongly controls the coupled suite of hydrodynamic processes. In contrast to fully dissipative surf zones, the bar-trough surf zone is not at all saturated and oscillations at incident wave frequency remain dominant from the break point to the subaerial beach. The degree of incident wave groupiness does not change appreciably across the surf zone. Infragravity standing waves which, in dissipative surf zones, dominate the inshore energy, remain energetically secondary and occur at higher frequencies in the bar trough surf zone. Analyses of the field data combined with numerical simulations of leaky mode and edge wave nodal—antinodal positions over observed surf-zone profiles, indicate that the frequencies which prevail are favored by the resonant condition of antinodes over the bar and nodes in the trough. Standing waves which would have nodes over the bar are suppressed. Sediment resuspension in the surf zone appears to be largely attributable to the incident waves which are the main source of bed shear stress. In addition, the extra near-bottom eddy viscosity provided by the reformed, non-breaking waves traversing the trough significantly affects the vertical velocity profile of the longshore current. Whereas the bar is highly mobile in terms of onshore—offshore migration rates, the beach face and inner regions of the trough are remarkably stable over time.     

Extension of the Narmada — Son lineament on the continental margin off Saurashtra,Western India as obtained from magnetic measurements

Magnetic total intensity values and bathymetric data collected on the continental margin off Saurashtra were, used to prepare magnetic anomalies and bathymetric contour maps. The magnetic anomalies are considered to have been caused by the Deccan Trap flood basalts which underlie the Tertiary sediments. Interpretation of the magnetic data using two-dimensional modelling method suggests that the magnetic basement is block faulted and deepens in steps from less than 1.0 km in the north to about 8.0 km towards the southern portion of the study area. The WNW-ESE trending faults identified in the present study extend across the Saurashtra continental margin between Porbandar and Veraval and appear to represent a major linear tectonic feature. The relationship of these fault lineaments with the regional tectonic framework have been discussed to indicate that they conform better as the northern boundary faults of the Narmada rift graben on the continental margin off Saurashtra.     

HYCAT: Hybrid hydrofoil catamaran concept

A hybrid marine vehicle concept has been developed which utilizes a combination of static and dynamic support. This concept, termed HYCAT² for HYdrofoil CATamaran, combines a planing catamaran hull with two fully submerged hydrofoils mounted in tandem fore and aft. The hullform is developed by adding a high length/beam ratio, high deadrise sidehull along the keel of each catamaran demihull. The sidehull, which is the only portion immersed when operating foilborne, provides buoyancy support. Spray strips provide discontinuities which separate the flow and provide dynamic lift in addition to the hydrofoils. Stability in the heave, pitch and roll degrees of freedom is achieved through the displacement dependent sidehull buoyancy and the rate and displacement dependent lift developed by the spray strips and hydrofoils. A comprehensive series of model tests has been conducted to characterize the smooth and rough water performance.     

Photoadaptation of carboxylating enzymes and photosynthesis during a spring bloom

Properties of the light saturation curve of photosynthesis and ribulose-1,5-bisphosphate carboxylase (RuBPC) activity are shown to change qualitatively in a natural population of marine phytoplankton during a spring bloom. Evidence is presented to show that these changes constitute photoadapative responses to increasing irradiance. As irradiance increased during the bloom, both the level of light-saturated photosynthesis (P_m) and the initial slope of the light saturation curve (α = photosynthetic efficiency) increased whether those parameters were normalized to chlorophyll a concentration (P_m^b, α^b) or to cell numbers (P_m^c, α^c). The magnitudes of these changes were such that I_k (= P_m/α, the photoadaptation parameter) did not change, but I_m, the light intensity at which photosynthesis becomes saturated, increased. RuBPC activity, both chlorophyll a (RuBPC^b) and cell number normalized (RuBPC^c), also increased during the bloom. We suggest that these adaptations were achieved by simultaneously increasing the number of photosynthetic units, proportionately decreasing the photosynthetic unit size, and increasing both the concentrations of the enzymes of the dark reactions and possibly also of photosynthetic electron transport components.We also observed diminished levels of photoinhibition in the high light adapted cells late in the bloom and have suggested that this was a consequence of the same suite of physiological changes.In situ carbon fixation per cell increased during the bloom whereas no change occurred in this parameter when normalized to chlorophyll a concentration. Although these photoadaptive responses thus permitted carbon to be fixed in situ more rapidly per cell, at a constant efficiency with respect to investment of energy in the photosynthetic apparatus, they did not result in a change in growth rate. Based on consideratios of the role of time scale in physiological adaptation, however, it is suggested that the observed alterations in photosynthesis with increasing irradiance might permit a cell to more rapidly fill an energy quota for division, possibly an advantage in a mixing environment in which energy is patchily distributed, both spatially and temporalyy.Phosphoenolpyruvate carboxylase activity when normalized to chlorophyll a (PEPC^b) did not change during the bloom while chlorophyll a normalized dark carbon fixation decreased sharply and was quantitatively small compared to PEPC^b. On this basis and considering that RuBPC^b increased during the bloom, it is suggested that, although PEPC may be involved in dark carbon fixation, its most important quantitative role is probably an indirect one in light dependent photosynthesis.We have also considered the relevance of laboratory results on photoadaptation to interpretations of field studies and have suggested that batch culture studies must be treated with caution but that turbidistat and semi-continuous methods provide reasonable simulations of natural conditions.     

Sound velocity,density, and related properties along a transect across the Bay of Bengal

Physical properties, sound velocity and density of 95 core samples from ten locations along a transect (parallel to 15°N latitude) across the Bay of Bengal were measured. Results indicate that sound velocities range from 1,482 to 1,679 m/s (av: 1,583 m/s) and densities from 1,338 to 1,757 kg/m³ (av: 1,527 kg/m³). It has been observed that dark colored clays and sandy clays show higher values of sound velocity and density than the average values. A comparative study of the same with that of the sediment cores collected from the Norwegian basin, Mediterranean Sea, and Hatteras, Nares Abyssal plains, western North Atlantic Ocean was done.     

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.     

The behaviour of a Cu(II) ion selective electrode in seawater; copper consumption capacity and copper determinations

Determinations of copper consumption capacity (CuCs.C) and labile copper concentrations in surface coastal seawater, using a copper ion selective electrode (Cu-ISE) potentiometric method under predominantly diffusive conditions, are reported. For evaluation of the copper concentrations, the points of the endpoint contiguity zone of the CuCs.C titration curve were treated by an ISE multiple standard addition technique. The results were compared with those obtained by means of a Chelex-100 (calcic form) ‘batch’ procedure-potentiometric stripping analysis.The labile copper of the sample was determined at concentrations down to 10.70 nM with an average RSD of 12%, independent of the Cu-ISE employed. For adjacent subsamples, the mean CuCs.C values obtained for El Way seawater were equivalent to 81.05 and 48.00 nM copper, with an RSD of 4 and 7%, and for Isla Santa Maria seawater the value was equivalent to 70.27 nM copper, with an RSD of 7%. The theoretical approach of the electrode diffusive mechanism proposed, which would depend, fundamentally, on the adsorptive, complexing and reducing properties of the dissolved organic matter in the seawater sample, allows simultaneous analytical determination of CuCs.C and labile copper concentration in seawater.     

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.