Ocean wave energy harvesting with a piezoelectric coupled buoy structure

An expedient piezoelectric coupled buoy energy harvester from ocean waves is developed. The harvester is made of several piezoelectric coupled cantilevers attached to a floating buoy structure, which can be easily suspended in the intermediate and deep ocean for energy harvesting. In the buoy structure, a slender cylindrical floater is attached on a large sinker. The energy harvesting process is realized by converting the transverse ocean wave energy to the electrical energy via the piezoelectric patches mounted on the cantilevers fixed on the buoy. A smart design of the buoy structure is developed to increase the energy harvesting efficiency by investigation of the effects of the sizes of the floater and the sinker. A numerical model is presented to calculate the generated electric power from buoy energy harvester. The research findings show that up to 24 W electric power can be generated by the proposed expedient buoy harvester with the length of the piezoelectric cantilevers of 1 m and the length of the buoy of 20 m. The technique proposed in this research can provide an expedient, feasible and stable energy supply from the floating buoy structure.     

Wave climate scatter performance of a cycloidal wave energy converter

A lift based cycloidal wave energy converter (WEC) was investigated using potential flow numerical simulations in combination with viscous loss estimates based on published hydrofoil data. This type of wave energy converter consists of a shaft with one or more hydrofoils attached eccentrically at a radius. The main shaft is aligned parallel to the wave crests and submerged at a fixed depth. The operation of the WEC as a wave-to-shaft energy converter interacting with straight crested waves was estimated for an actual ocean wave climate. The climate chosen was the climate recorded by a buoy off the north-east shore of Oahu/Hawaii, which was a typical moderate wave climate featuring an average annual wave power P_W = 17 kWh/m of wave crest. The impact of the design variables radius, chord, span and maximum generator power on the average annual shaft energy yield, capacity factor and power production time fraction were explored. In the selected wave climate, a radius R = 5 m, chord C = 5 m and span of S = 60 m along with a maximum generator power of P_G = 1.25 MW were found to be optimal in terms of annual shaft energy yield. At the design point, the CycWEC achieved a wave-to-shaft power efficiency of 70%. In the annual average, 40% of the incoming wave energy was converted to shaft energy, and a capacity factor of 42% was achieved. These numbers exceeded the typical performance of competing renewables like wind power, and demonstrated that the WEC was able to convert wave energy to shaft energy efficiently for a range of wave periods and wave heights as encountered in a typical wave climate.     

Fish settlement in the ocean vs. estuary: Comparison of pelagic larval and settled juvenile composition and abundance from southern New Jersey,U.S.A.

To describe the larval and juvenile fish fauna and to evaluate the relative contribution of the ocean and the estuary as settlement areas for benthic species, we compared the composition and abundance of larval fish supply to that of recently settled juvenile fishes in both ocean and an adjacent estuary habitats in southern New Jersey. The study was conducted from May to November 1992 in the Great Bay–Little Egg Harbor estuary (<1–8 m sampling depth) and on the adjacent inner continental shelf in the vicinity of Beach Haven Ridge (8–16 m). During the study more larvae nearing settlement (postflexion) were captured in the estuary than in the ocean. Settlement occurred earlier in the estuary than in the ocean perhaps under the influence of earlier, seasonal warming of estuarine waters. There appeared to be two spatial patterns of settlement in the study area based on the dominant species (n = 17) represented by a sufficient number of individuals (n ≥ 25 individuals). There were species that primarily settle in the estuary, as represented by both estuarine residents (n = 3) and transients (n = 4), and those that settle in both the estuary and the ocean (n = 10). However, there were no species whose larvae were present in the estuary yet settle in the ocean. The fact that many of the species settle in both the estuary and the ocean indicates an overlap between these habitats because, at least for some species, these habitats may function in the same way. Further resolution of fish settlement patterns, and its influence on recruitment will need to rely on synoptic comparisons between estuaries and the ocean over multiple years.     

The effect of yaw angle on VIV suppression for an inclined flexible cylinder fitted with helical strakes

Experimental studies were carried out to investigate the response features of an inclined flexible bare cylinder as well as a straked cylinder in a towing tank, with the main purpose of further improving the understanding of the effect of yaw angle on vortex-induced vibration (VIV) suppression. Four yaw angles (a = 0°, 15°, 30°, 45°), which is defined as the angle between the cylinder axis and the plane orthogonal to the oncoming fluid flow, were tested. The cylinder model was towed along the tank to generate a uniform fluid flow. The towing velocity was in the range of 0.05–1.0 m/s with an interval of 0.05 m/s. The corresponding Reynolds number ranged from 800 to 16000. The strakes selected for the experiments had a pitch of 17.5D and a height of 0.25D, which is generally considered as the most effective configuration for VIV suppression of a flexible cylinder in water. The experimental results indicate that VIV suppression effectiveness of the inclined flexible straked cylinder is closely related to the yaw angle. The displacement amplitudes are significantly suppressed in both cross-flow (CF) and in-line (IL) directions at a = 0°. However, with increasing yaw angle, the suppression efficiencies of the CF and IL displacement amplitudes gradually decrease. In addition, the CF dominant frequencies of the straked cylinder obviously deviate from those of the bare cylinder at a = 0° and 15°. This deviation is substantially alleviated with increasing yaw angle. The IL dominant frequencies show less dependency on the yaw angle. Similar trends are also observed on the dominant modes of vibration and the mean drag coefficients.     

Force and flow characteristics of a circular cylinder with uniform surface roughness at subcritical Reynolds numbers

The main purpose of this study is to establish a better understanding of the relationship between drag reduction and surface roughness. Experiments were conducted to measure the force and flow characteristics of a circular cylinder with different types of artificial surface roughness over the range 6 × 10³ < Re < 8 × 10⁴ (Re is based on the cylinder diameter D). The roughness cylinder was formed by covering the exterior surface of the cylinder with uniformly distributed (1) sandpaper, (2) netting, and (3) dimples. The roughness coefficient ranged from k/D = 0.0028 to 0.025 (k is the roughness height). A detailed quantitative measurement of the flow field around the cylinder using Particle Imaging Velocimetry (PIV) was carried out. The hydrodynamic force coefficients (drag and lift) of the rough cylinders are compared against those of a smooth cylinder measured under the same flow conditions. It is found that certain configuration of surface roughness significantly reduces the mean drag coefficient of the cylinder, particularly at large Reynolds numbers. In addition, the root-mean-square (r.m.s.) lift coefficient of the rough cylinders is considerably lower than that of a smooth cylinder.     

Numerical investigation on the suppression of VIV for a circular cylinder by three small control rods

Laminar flow past a circular cylinder with 3 small control rods is investigated by numerical simulation. This study is concerned with the suppression efficacy of vortex induced vibration by small control rods located around a main cylinder. The effects of the attack angle and rod-to-cylinder gap ratio on the hydrodynamics and vibration responses of the main cylinder are investigated. The attack angle of α = 45° is performed as the critical angle for VIV suppression of 3 control rods. The 3 control rods have no effect on VIV suppression when the attack angle is less than the critical angle. The 3 control rods have an excellent VIV suppression efficacy when the attack angle is larger than the critical angle. The transverse vibration frequency of the cylinder with 3 control rods is less than that for an isolated cylinder for all the configurations. The numerical results for the configurations of α = 45° & 60°, G/D = 0.6–1.2 show excellent suppression efficient among the cases investigated in this study. The best suppression efficient is found at α = 45°, G/D = 0.9 for 3 control rods. 2 rods in behind of the main cylinder perform more efficient than that of 1 rod in front for VIV suppression as the gap ratio of G/D less than 1.0.     

Computations of the energy flux to mixing processes via baroclinic wave drag on barotropic tides

The geographical distribution of barotropic to baroclinic transfer of tidal energy by baroclinic wave drag in the abyssal ocean is estimated. Using tidal velocities from a state-of-the-art numerical tidal model, the total loss of barotropic tidal energy in the deep ocean (between 70°S and 70°N and at depths greater than 1000 m) is estimated to be about 0.7 TW (M₂) corresponding to a mean value of the energy flux (e) of 2.4×10⁻³ W/m². The distribution of e is however highly skewed with a median of about 10⁻⁶ W/m². Only 10% of the area is responsible for more than 97% of the total energy transfer.To assess the possible influence of the relatively coarse bathymetry representation upon the present estimate, complementary calculations using better resolved sea floor topography are carried out over a control area around the Hawaiian Ridge. There are no major differences between the results achieved using the two different bathymetry databases. Fluxes of about 16 GW or 6×10⁻³ W/m² are computed in both cases, and the main contributions to the total fluxes originate in the same range of e-values and cover equally large parts of the total area.It is not clear whether the present model is valid at flat or subcritical bottom slopes. However, for the Hawaiian region, only 2% of the total energy flux as calculated in the present study originates in areas of critical and subcritical slopes.     

Flow induced vibrations of a sharp edge square cylinder in the wake of a circular cylinder

The response of an oscillating circular cylinder at the wake of an upstream fixed circular cylinder was classified by different researchers as galloping, wake induced galloping or wake induced vibration. Furthermore it is already known that a sharp edge square cylinder would undergo galloping if it is subjected to uniform flow. In this study the influence of the wake of a fixed circular cylinder on the response of a downstream square cylinder at different spacing ratios (S/D = 4, 8, 11) is experimentally investigated. The subject appears not to have received previous attention. The lateral displacements, lift forces and the pressure data from gauges mounted in the wake of the oscillating cylinder are recorded and analyzed. The single degree of freedom vibrating system has a low mass-damping parameter and the Reynolds number ranges from 7.7 × 10² to 3.7 × 10⁴.In contrast to that for two circular cylinders in tandem arrangement, the freely mounted downstream square cylinder displays a VIV type of response at all spacing ratios tested. There is no sign of galloping or wake induced galloping with the square cylinder. With increase at the spacing ratio the cross-flow oscillations decrease. It is shown that the vortices arriving from the upstream fixed circular cylinder play a major role on the shedding mechanism behind the downstream square cylinder and cause the square cylinder to shed vortices with frequencies above Strouhal frequency of the fixed square cylinder (St = 0.13). The VIV type of oscillations in the downstream square cylinder is most probably caused by the vortices newly generated behind the square cylinder.     

Aggregation of the Arctic copepod Calanus hyperboreus over the ocean floor of the Greenland Sea

According to combined observations from vertical plankton tows, dredging with epibenthic nets 1 m above the ocean floor, video recordings and acoustic data from a scanning sonar obtained during descent and during deployment on the ocean floor, the calanoid copepod Calanus hyperboreus was aggregated in high concentrations near the ocean floor of the Greenland Sea between 2300 and 2500 m during late July and August. Concentrations were highest very close to the ocean floor and decreased rapidly further upward. These nearly mono-specific aggregations were apparently drifting in cloud-like formations with a horizontal extension of ca. 270 m with the near-bottom currents. Maximum abundances observed were up to 2 orders of magnitude higher than in the water column. The biomass in the bottom 20 m layer was around 18% of the biomass in the rest of the water column. Stage composition, reduced metabolic rates and insensibility to mechanical stimuli indicate that these C. hyperboreus were representing the resting population. The fact that high concentrations were observed during deployments lasting >1 d and in 3 years suggests that aggregation near the ocean floor is a regular, rather than an extraordinary, pattern in the life history of C. hyperboreus in the Greenland Sea, but there is need for comparison with other seas and eventually other Calanus species.     

The validity of the independence principle applied to the vortex-induced vibration of an inclined cylinder in steady flow

The validity of the independence principle applied to the vortex-induced vibration (VIV) of an inclined cylinder in steady flow is investigated by conducting numerical simulations. In order to create a perfect end-effect-free condition, periodic boundary condition is applied on the two end boundaries that are perpendicular to the cylinder. It is found that the response amplitude and frequency for an inclination angle of α = 45° agree well with their counterparts for α = 0°. The numerical results demonstrated the validity of the independence principle in the case of vortex-induced vibration, which has not been demonstrated by laboratory tests due to the difficulty in avoiding the end effects.     

Mode-1 internal tides in the western North Atlantic Ocean

Mode-1 internal tides were observed the western North Atlantic using an ocean acoustic tomography array deployed in 1991–1992 centered on 25°N, 66°W. The pentagonal array, 700-km across, acted as an antenna for mode-1 internal-tides. Coherent internal-tide waves with O(1 m) displacements were observed traveling in several directions. Although the internal tides of the region were relatively quiescent, they were essentially phase locked over the 200–300 day data record lengths. Both semidiurnal and diurnal internal waves were detected, with wavenumbers consistent with those calculated from hydrographic data. The M₂ internal-tide energy flux was estimated to be about 70 W m⁻¹, suggesting that mode-1 waves radiate 0.2 GW of energy, with large uncertainty, from the Caribbean island chain at this frequency. A global tidal model (TPXO 5) suggested that 1–2 GW is lost from the M₂ barotropic tide over this region, but the precise value was uncertain because the complicated topography makes the calculation problematic. In any case, significant conversion of barotropic to baroclinic tidal energy does not occur in the western North Atlantic basin. It is apparent, however, that mode-1 internal tides have very weak decay and retain their coherence over great distances, so that ocean basins may be filled up with such waves. Observed diurnal amplitudes were an order of magnitude larger than expected. The amplitude and phase variations of the K₁ and O₁ constituents observed over the tomography array were consistent with the theoretical solutions for standing internal waves near their turning latitude. The energy densities of the resonant diurnal internal waves were roughly twice those of the barotropic tide at those frequencies.     

Experimental study of interactions between multi-directional focused wave and vertical circular cylinder,part II: Wave force

We describe experiments with multi-directional focused waves interacted with a vertical circular cylinder in a 3D wave basin. The focus of this study is on the run-up of multi-directional focused waves, wave forces, and wave pressures on the cylinder. Part I, the study on wave run-up, has already been presented by Li et al. (2012). In this paper, the analysis of the wave force on the vertical cylinder is presented.In this experiment, a cylinder with 0.25 m in diameter was adopted and different wave parameters, such as focused wave amplitude, peak frequency, frequency bandwidth and directional spreading index, are considered. The model scale k_pa (k_p is the wave number corresponding to peak frequency, a is the radium of the cylinder) varies from 0.32 to 0.65. The maximum forces of multi-directional focused wave on cylinder were measured and investigated. The results showed that the wave parameters have a significant influence on the wave force, and that the spatial profile of the surface of multi-directional focused wave can also affect its force on the cylinder, which is different from two-dimensional wave. In addition, the ‘secondary loading cycle’ phenomenon was also observed and discussed. In our experiments, the ‘secondary loading cycles’ occur when kA > 0.36 for all cases. While in some referred small scale experiments, the secondary load cycles are observed even for kA = 0.2, when the waves are longer enough. To larger model scale, the pronounced secondary load cycle occurs with larger wave steepness waves.     

Bioenergetic model estimates of interannual and spatial patterns in consumption demand and growth potential of juvenile pink salmon (Oncorhynchus gorbuscha) in the Gulf of Alaska

A bioenergetic model of juvenile pink salmon (Oncorhynchus gorbuscha) was used to estimate daily prey consumption and growth potential of four ocean habitats in the Gulf of Alaska during 2001 and 2002. Growth potential was not significantly higher in 2002 than in 2001 at an alpha level of 0.05 (P=0.073). Average differences in growth potential across habitats were minimal (slope habitat=0.844 g d⁻¹, shelf habitat=0.806 g d⁻¹, offshore habitat=0.820 g d⁻¹, and nearshore habitat=0.703 g d⁻¹) and not significantly different (P=0.630). Consumption demand differed significantly between hatchery and wild stocks (P=0.035) when examined within year due to the interaction between hatchery verses wild origin and year. However, the overall effect of origin across years was not significant (P=0.705) due to similar total amounts of prey consumed by all juvenile pink salmon in both study years. We anticipated that years in which ocean survival was high would have had high growth potential, but this relationship did not prove to be true. Therefore, modeled growth potential may not be useful as a tool for forecasting survival of Prince William Sound hatchery pink salmon stocks. Significant differences in consumption demand and a two-fold difference in nearshore abundance during 2001 of hatchery and wild pink salmon confirmed the existence of strong and variable interannual competition and the importance of the nearshore region as being a potential competitive bottleneck.     

Solitary wave generation dynamics at Luzon Strait

A high resolution modeling study is undertaken, with a 2.5-dimensional nonhydrostatic model, of the generation of internal waves induced by tidal motion over the ridges in Luzon Strait. The model is forced by the barotropic tidal components K1, M2, and O1. These tidal components, along with the initial density field, were extracted from data and models. As the barotropic tide moves over the Luzon Strait sills, there is a conversion of barotropic tidal energy into baroclinic tidal energy. Depressions are generated that propagate towards the Asian Seas International Acoustics Experiment (ASIAEX) test site on the Chinese continental shelf. Nonlinear effects steepen the depressions, frequency and amplitude dispersion set in, and disintegration into large amplitude solitary waves occurs. The effects of varying the initial density field, tidal component magnitudes, as well as adding a steady background current to represent the occasional excursions of the Kuroshio Current into the strait, are considered.Depressions are generated at each of the two sills in Luzon Strait which radiate away, steepening and evolving into internal solitary wave trains. Baroclinic fluxes of available potential energy, kinetic energy and linear are calculated for various parameter combinations. The solitary wave trains produced in the simulations generally consist of large amplitude wave trains alternating with small amplitude wave trains. During strong tidal flow, Kelvin–Helmholtz type instabilities can develop over the taller double-humped sill. The solitary waves propagating towards the ASIAEX test site have been observed to reach amplitudes of 120–250 m, depending on the tidal strength. ASIAEX observations indicate amplitudes up to 150 m and the Windy Island Experiment (WISE) measurements contain magnitudes over 200 m. The model results yield solitary wave amplitudes of 70–300 m and half widths of 0.60–3.25 km, depending on parameter values. These are in the range of observations. Measurements by Klymak et al. (2006), in the South China Sea, exhibit amplitudes of 170 m, half widths of 3 km and phase speeds of 2.9 m s^?1. Model predictions indicate that the solitary waves making up the wave packet each experience different background currents with strong near surface shear.The energy in the leading soliton of the large amplitude wave trains ranges between 1.8 and 9.0 GJ m^?1. The smaller value, produced using barotropic tidal currents based on the Oregon State University data base, is the same as the energy estimated to be in a solitary wave observed by Klymak et al. (2006). Estimates of the conversion of barotropic tidal energy into radiating internal wave energy yield conversion rates ranging between 3.6% and 8.3%.     

Numerical simulations of wave–current flow in an ocean basin

Wave–current flow is a phenomenon that is present in many practical engineering situations. Over the past several decades, this type of flow has been increasingly investigated under controlled laboratory conditions. This paper presents a numerical study of wave–current flow in the ocean basin of the LabOceano (COPPE/UFRJ). A homogeneous multiphase model based on the RANS equations and the k–ɛ turbulence model implemented in ANSYS-CFX code were used. A cross section of the ocean basin was represented. A regular wave with a height of 0.08 m and a period of 1.80 s (i.e., a wave steepness of H/L = 0.016), propagating on favourable currents, was simulated. The behaviour of the free surface elevation over time and the streamlines along the basin for wave and wave–current flows were presented. The numerical results were compared to the non-viscous theory given by the Rayleigh equation applied to the problem of wave–current interaction. Good agreement was found between the wave length estimated by the numerical results and the analytical solutions, with a deviation of less than 2%.     

The role of crabs (Macrophthalmus japonicus) burrows on organic carbon cycle in estuarine tidal flat,Japan

The objective of this study is to elucidate the burrow structure and to clarify the role of burrows in material cycle in the tidal flat. In our work, we focused on the dominant species in muddy tidal flat, crab Macrophthalmus japonicus.Burrow structure of Macrophthalmus japonicus was investigated on a Katsuura river tidal flat in Tokushima prefecture, Japan, using in situ resin casting. Sampling was conducted in August 2006, and a total of 48 burrow casts were obtained. Burrows consisted mainly of J-shaped structures (98%) while the rest belonged to U-shaped structures (2%). The maximum measured burrow volume was 120 cm³ and wall surface area was 224 cm², while maximum burrow length and depth were 23.2 cm and 16.5 cm, respectively. Burrow volume and surface area were strongly correlated with carapace width of M. japonicus. Investigation of the individual number of M. japonicus in 13 quadrats (50 × 50 × 20 cm) was conducted using 2 mm sieve. The number of M. japonicus was 15–31 ind./m². Using cohort analysis we estimated that surface area of burrows was 0.07–0.15 m²/m².CO₂ emission rate was measured at the surface sediment during the period from June to December 2008. Results varied from 13.8 ± 2.2 to 49.4 ± 3.2 mg CO₂/m²/h, and organic carbon decomposition was 3.8 ± 0.6–13.5 ± 0.9 mg C/m²/h. This leads the increase of organic carbon decomposition by 1.1 times, because of the expansion of the tidal flat surface area by burrowing activity. Organic carbon decomposition in burrow walls therefore contributed to organic matter decomposition in the tidal flat. These results indicated that in situ activities of Macrophthalmus japonicus significantly influence the material cycle and it is important to consider the existence of burrow in order to understand the fluxes of materials and to evaluate the purification function of the tidal flat.     

Submarine groundwater discharge (SGD) as a main nutrient source for benthic and water-column primary production in a large intertidal environment of the Yellow Sea

The biogeochemistry and magnitude of submarine groundwater discharge (SGD) was investigated in one of the largest tidal flat ecosystems worldwide, along the Yellow Sea coast. A representative semi-enclosed embayment located in the south eastern Yellow Sea, Hampyeong Bay, was chosen for this purpose. Groundwater and seawater samples were collected in three seasons (May, July, and September) and analyzed for Ra isotopes, nutrients, and photosynthetic pigments. The biogeochemistry of SGD was strongly influenced by tidal oscillations and seasonal precipitation changes and switched from a brackish, nutrient-enriched regime in May and July to an exclusively saline regime, with lower nutrient concentrations, in September. SGD magnitudes, calculated by using a ²²⁶Ra mass balance model, were 0.14 m³ m^? 2 d^? 1 in May and 0.35 m³ m^? 2 d^? 1 in September. A nutrient mass balance was established for the two campaigns, which suggests that SGD causes the flushing of substantial amounts of pore water nutrients into this embayment; because of SGD, the embayment acts as a source of dissolved inorganic silicates (DSi) that are transported to the open ocean. Potential C fixation rates derived from this nutrient mass balance were compared with two different models for water-column phytoplankton productivity based on water-column Chl a and local irradiation levels. The Chl a-based models generally showed lower C fixation rates than the nutrient-based mass balance, indicating removal of up to 70% of the nutrients by other primary producers, such as benthic algae. During monsoon season, when benthic algal biomass is high and nutrient fluxes are substantial due to a terrestrial component, SGD — driven benthic primary production could play a significant role in this large tidal flat ecosystem.     

Investigation of drag crisis phenomenon using CFD methods

When fluid flow passes a cylinder, the drag crisis phenomenon occurs between the sub-critical and the super-critical Reynolds numbers. The focus of the present studies was on the numerical prediction of the drag crisis based on CFD methods. In this work, block structured meshes with refined grids near the cylinder surface and in the downstream were employed. Both 2D and 3D simulations were performed using various turbulence models, including the SST k − ω model, the k − ϵ model, the SST with LCTM, the DES model, and the LES model. In the convergence studies, the effects of the grid size, the time step, the first grid size and the aspect ratio (for 3D simulations) on the solutions were examined. The errors due to spatial and time discretizations were quantified according to a V&V procedure. Validation studies were carried out for various Reynolds numbers between Re = 6.31 × 10⁴ and 7.57 × 10⁵. The averaged drag force, the RMS of lift force and the Strouhal number were compared with experimental data. The studies indicated that standard 2D and 3D RANS methods were inadequate to capture the drag crisis phenomenon. The LES method however has the potential to address the problem.     

Respiration,mineralization, and biochemical properties of the particulate matter in the southern Nansen Basin water column in April 1981

Determinations of the activity of the respiratory electron transport system (ETS), during the FRAM III expedition permit us to estimate oxygen utilization rates (R_O2) from the surface to 2000 m under the polar pack ice in the Nansen Basin just north of Svalbard (83°N, 7°E) during April 1981. We found R_O2 at in situ temperatures ranging from 20 pM O₂ min⁻¹ just below the ice to 0.2 pM O₂ min⁻¹ at 2000 m. These rates are low compared to most other ocean regions, but they could decrease particulate organic carbon and nitrogen by 76% and 74%, respectively, over a period of ∼6 months. The R_O2 calculations based on measurements made at 0 °C yielded a power function of R_O2 vs. depth (Z) of R_O2=67Z^−0.5534. When this R_O2 profile was superimposed on a more recent oxygen utilization rate profile made using the ³He–³H–AOU method (OUR), in the same vicinity of the Nansen Basin during 1987 (OUR=52Z^–0.4058, [Zheng, Y., Schlosser, P., Swift, J.W., Jones, E.P., 1997. Oxygen utilization rates in the Nansen Basin, Arctic Ocean: implications for new production. Deep Sea Research I 44, 1923–1943]), the agreement of the two profiles was close. On one hand, this was to be expected because R_O2 is the biological basis of OUR, on the other hand, it was a surprise because the methodologies are so different. Nitrate mineralization obtained from ETS activities also compared favorably with calculations based on the data of Zheng et al. [1997. Oxygen utilization rates in the Nansen Basin, Arctic Ocean: implications for new production. Deep Sea Research I 44, 1923–1943]. Chlorophyll ranged from 6 ng L⁻¹ at 5 m to 0.06 ng L⁻¹ at 2000 m. Particulate organic carbon (POC) decreased from 0.93 μM C just below the ice to less than 0.4 μM C at 500 m. Particulate organic nitrogen (PON) was not detectable below 70 m, however in the upper 70 m it ranged from 0.16 to 0.04 μM N. The C/N mass ratio over these depths ranged from 5.8 to 11.3. Annual carbon productivity as calculated to balance the total water column respiration was 27 g C m⁻² y⁻¹. The integrated respiration rate between 50 and 4000 m suggests that exported production and carbon flux from the 50 m level was 24 g C m⁻² y⁻¹. These are minimal estimates for the southern Nansen Basin because they are based on measurements made at the end of the Arctic winter.     

Kinetic study reveals weak Fe-binding ligand,which affects the solubility of Fe in the Scheldt estuary

The chemistry of dissolved Fe(III) was studied in the Scheldt estuary (The Netherlands). Two discrete size fractions of the dissolved bulk (< 0.2 μm and < 1 kDa) were considered at three salinities (S = 26, 10 and 0.3).Within the upper estuary, where fresh river water meets seawater, the dissolved Fe concentration decreases steeply with increasing salinity, for the fraction < 0.2 μm from 536 nM at S = 0.3 to 104 nM at S = 10 and for the fraction < 1 kDa from 102 nM to 36 nM Fe. Further downstream, in the middle and lower estuary, this decrease in the Fe concentration continues, but is far less pronounced. For all samples, the traditionally recognised dissolved strong organic Fe-binding ligand concentrations are lower than the dissolved Fe concentrations.Characteristics of dissolved Fe-binding ligands were determined by observing kinetic interactions with adsorptive cathodic stripping voltammetry. From these kinetic experiments we concluded that apart from the well-known strong Fe-binding organic ligands (L, logK′ = 19–22) also weak Fe-binding ligands (P) existed with an α value (binding potential = K′ · [P]) varying between 10^11.1 and 10^11.9. The presence of this relatively weak ligand explained the high concentrations of labile Fe present in both size fractions in the estuary. This weak ligand can retard or prevent a direct precipitation after an extra input of Fe.The dissociation rate constants of the weak ligand varied between 0.5 × 10^− 4 and 4.3 × 10^− 4 s^− 1. The rate constants of the strong organic ligand varied between k_d = 1.5 × 10^− 3–17 × 10^− 2 s^− 1 and k_f = 2.2 × 10⁸–2.7 × 10⁹ M^− 1 s^− 1. The dissociation rate constant of freshly amorphous Fe-hydroxide was found to be between 4.3 × 10^− 4 and 3.7 × 10^− 3 s^− 1, more labile or equal to the values found by Rose and Waite [Rose, A.L., Waite, T.D., 2003a. Kinetics of hydrolysis and precipitation of ferric iron in seawater. Environ. Sci. Technol., 37, 3897–3903.] for freshly precipitated Fe in seawater.Kinetic rate constants of Fe with the ligand TAC (2-(2-Thiazolylazo)-p-cresol) were also determined. The formation rate constant of Fe(TAC)₂ varied between 0.1 × 10⁸ and 3.6 × 10⁸ M^− 1 s^− 1, the dissociation rate constant between 0.2 × 10^− 5 and 17 × 10^− 5 s^− 1 for both S = 26 and S = 10. The conditional stability constant of Fe(TAC)₂ (β_Fe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβ_Fe(TAC)2′ = 22.4; [Croot, P.L., Johansson, M., 2000. Determination of iron speciation by cathodic stripping voltammetry in seawater using the competing ligand 2-(2-Thiazolylazo)-p-cresol (TAC). Electroanalysis, 12, 565–576.]). However, at S = 0.3 the logβ_Fe(TAC)2′ was 25.3, three orders of magnitude higher. Apparently the application of TAC to samples of low salinity can only be done when the correct β_Fe(TAC)2′ is known.