Experimental investigation of blade and propeller loads: Steady turning motion

This paper is the continuation of the work described in [14], dedicated to the presentation of the results of propeller performance in behind-hull during straight ahead motion obtained by a novel experimental set-up for the measurements of single blade loads. In the present case, the study shows and discusses the single blade and propeller loads developed during steady turning conditions, that were simulated by means of free running, self propelled maneuvering tests for a twin screw configuration. Maneuvering conditions are critical for the ship propulsion system, because the performance of the propeller and the side effects related to its functioning (propeller–hull induced pressure and vibrations, noise) are completely different with respect to the design condition in straight ahead motion. Thrust and torque and generation of in-plane loads (force and moments), developed by the blade during the period, evolve differently for the two propellers, due to different propeller–wake interactions. The understanding and the accurate quantification of propeller loads, in these realistic operative scenarios, are pivotal to design low emission and comfortable ships, fulfilling the requirements of safety and continuity of operations at sea. The analysis is carried out revisiting the investigation in [14] for three different speeds (F_N = 0.26, 0.34 and 0.40) and a large set of rudder angles that span moderate and tight maneuvers.     

Numerical investigation of the scale effect of hydrodynamic performance of the hybrid CRP pod propulsion system

The scale effect of hydrodynamic performance of the hybrid CRP pod propulsion system was investigated numerically using the RANS method combined with SST k − ω turbulence model and moving mesh method. The pod resistance influence factor was introduced to represent the effect of wake field of CRP on the pod resistance. Results showed the pod resistance influence factor to be a function of the Reynolds number and revolution ratio. Representative function expression can be obtained by regression analysis using multiplication of multinomial polynomials and linear function. The standard ITTC 1978 extrapolation procedure can be utilized to predict hydrodynamic performance of forward propeller because of the slightness of the influence of the pod unit on the forward propeller. The thrust and torque coefficient influence factors of aft propeller were introduced, and they were found to represent the effect of wake field of forward propeller and blockage effect of the pod on the hydrodynamic performance of aft propeller. It shows that thrust and torque coefficient influence factors are independent of the Reynolds number and have a linear relationship with the revolution ratio. On this basis, a method of estimating the hydrodynamic performance was proposed for full scale propulsion system.     

Unsteady RANS simulation of a surface piercing propeller in oblique flow

Conventional propellers might undergo severe cavitation at high speeds and this phenomenon not only affects the efficiency of the propeller, but also may result in serious damages in propulsion system. Due to their special geometries, surface piercing propellers (SPPs) overcome this problem and achieve high efficiencies in high speeds. Therefore, SPPs are one of the popular propulsors for high-speed crafts. The present research is aimed to pursue SPP's performance in the off-design conditions. URANS method was used to study the performance of the 841-B SPP (a case with some available experimental results; Olofsson, 1996) in several immersion ratios (I = 33%, 50%, 75% and 100%) and maneuvering conditions (incident angles of 0°, 10° and 20°). The free surface was simulated using VOF method. Off-design conditions might exert extra or less forces and torques on the propeller's blade. In the present research for 841-B SPP, it was found that a maneuver condition would increase the thrust and torque coefficient for some cases. The sliding mesh technique was utilized to simulate the 841-B SPP performance, which unlike the multiple reference frame (MRF) technique, this technique allows to capture the blades hit on the water surface in transient mode simulations.     

Investigation of a longfin inshore squid's swimming characteristics and an underwater locomotion during acceleration

In the present study, locomotion of a real longfin inshore squid (Doryteuthis pealeii) was numerically investigated. Geometry of a real squid was obtained using computed tomography (CT) images. In addition to a two-dimensional axisymmetric squid model, a modified squid model with no cavities around her head and an ellipse shaped model were generated with a fineness ratio (the ratio of body length to maximum body diameter) of 7.56. These numerical models were exposed to an acceleration with two different velocity programs. Added mass and basset forces on bodies were calculated during acceleration of the squid models starting from rest. Pressure and viscous drag forces were also calculated due to pressure variation along the squid models and friction on the surface of the models. The effect of a nozzle diameter on jet velocities and propulsive efficiency at all bodies were evaluated when time dependent velocity profiles (from 0 to 10 m/s in 0.5 and 1 s time durations) were set for the inlet of computational domain. The modified squid model required least thrust force during acceleration phase of time dependent velocity profile compared to the other models while the 0.02 m nozzle diameter provided largest propulsive efficiency for all models.     

Energy performance evaluation of fishing vessels by fuel mass flow measuring system

A new fuel consumption monitoring system was set up for research purpose in order to evaluate the energy performance of fishing vessels under different operating conditions. The system has been tested on two semi-pelagic pair trawlers in the Adriatic Sea with an engine power of around 900 kW, and with length overall of around 30 m. Both vessels work with a gear of similar design and size, the differences between the two vessels are in the propeller design and the hull material: the first with a controllable pitch propeller (CPP) and a metal hull, the second with a fixed pitch propeller (FPP) and a wooden hull. The fuel monitoring system conceived at CNR-ISMAR Ancona (Italy) consists of two mass flow sensors, one multichannel recorder and one GPS data logger. The working time duration, the vessel speed, the total fuel consumption and the instant fuel rate were logged by the system. A typical commercial round trip for a semi-pelagic trawler consists of several fishing operations (steaming, trawling sailing, etc.). Fuel consumption rate and vessel speed data were used to identify energy performance under different vessel-operating conditions. The highest fuel demands were during the trawling (130 l/h at 4.4 kn) and the steaming (100–130 l/h at 11 kn) phases. Fuel savings of up to 15% could be obtained by reducing the navigation speed of half a knot.     

Scour depth under pipelines placed on weakly cohesive soils

We here study the scouring processes that evolve around a submarine pipeline placed on a weakly cohesive seabed. We first analyze some laboratory tests carried out by Vijaya Kumar et al. [21], Xu et al. [25] and Zhou et al. [28] that focused on the scouring around a horizontal cylinder lying on a cohesive bed, subject to waves and currents. The specific purpose is that of finding a new formula for the prediction of the equilibrium scour depth under submarine pipelines. After a theoretical analysis of the main parameters, the sought formula has been found to be a function of: (i) the hydrodynamic forces acting on the cylinder (through the Keulegan–Carpenter parameter KC), (ii) the clay content of the soil C_c, and (iii) the burial depth e₀/D. In the presence of small amounts of clay (C_c< 5 %), the scour depth depends directly on KC (as confirmed by many literature works for pipelines lying on sandy soils, e.g. [18]) and inversely on C_c (as already seen for bridge abutments on cohesive soils, e.g. [1]), the best-fit law being characterized by a coefficient of determination R² = 0.62. If some burial depth is accounted for, this being a novelty of the present work, a more general formulation can be used, valid in the presence of weakly-cohesive soils and with burial depths of the pipe smaller than 0.5 (R² = 0.79). For large clay-content ranges (2% < C_c < 75 %), the scour depth depends directly on both KC and C_c, this giving R² = 0.79 (no burial depth) and 0.91 (some burial depth). However, this finding is at odds with the main literature, because, for large amounts of clay, it is fundamental to consider the liquidity index LI, which accounts for some important clay properties, like the plasticity. We argue that the absence of LI is balanced by the direct dependence of the scour depth on C_c. Notwithstanding the small number of available data, a formula for the prediction of the scour depth under pipelines lying on cohesive soils is fundamental for several engineering applications. The present contribution represents the first attempt to build such a formula, when the pipeline is subject to the wave-current forcing and the seabed is characterized by a relatively small clay content.     

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.     

Narrow banded wave propagation from very deep waters to the shore

A fully nonlinear Boussinessq-type model with several free coefficients is considered as a departure point. The model is monolayer and low order so as to simplify numerical solvability. The coefficients of the model are here considered functions of the local water depth. In doing so, we allow to improve the dispersive and shoaling properties for narrow banded wave trains in very deep waters. In particular, for monochromatic waves the dispersion and shoaling errors are bounded by ~ 2.8% up to kh = 100, being k the wave number and h the water depth. The proposed model is fully nonlinear in weakly dispersive conditions, so that nonlinear wave decomposition in shallower waters is well reproduced. The model equations are numerically solved using a fourth order scheme and tested against analytical solutions and experimental data.     

Nutrient gradients in the western North Atlantic Ocean: Relationship to microbial community structure and comparison to patterns in the Pacific Ocean

Studies of nitrogen and phosphorus dynamics in the oligotrophic surface waters of the western North Atlantic Ocean have been constrained because ambient concentrations are typically at or below the detection limits of standard colorometric methods, except during periods of deep vertical mixing. Here we report the application of high-sensitivity analytical methods—determinations of nitrate plus nitrite (N+N) by chemiluminescence and soluble reactive phosphorus (SRP) by the magnesium induced co-precipitation (MAGIC) protocol—to surface waters along a transect from the Sargasso Sea at 26°N through the Gulf Stream at 37°N, including sampling at the JGOFS Bermuda Atlantic Time-series Study (BATS) station. The results were compared with data from the BATS program, and the HOT station in the Pacific Ocean, permitting cross-ecosystem comparisons. Microbial populations were analyzed along the transect, and an attempt was made to interpret their distributions in the context of the measured nutrient concentrations.Surface concentrations of N+N and SRP during the March 1998 transect separated into 3 distinct regions, with the boundaries corresponding roughly to the locations of the BATS station (∼31°N) and the Gulf Stream (∼37°N). Although N+N and SRP co-varied, the [N+N] : [SRP] molar ratios increased systematically from ∼1 to 10 in the southern segment, remained relatively constant at ∼40–50 between 31°N and 37°N, then decreased again systematically to ratios <10 north of the Gulf Stream. Dissolved organic N (DON) and P (DOP) dominated (⩾90%) the total dissolved N (TDN) and P (TDP) pools except in the northern portion of the transect. The [DON] : [DOP] molar ratios were relatively invariant (∼30–60) across the entire transect.Heterotrophic prokaryotes (operationally defined as “bacteria”), Prochlorococcus, Synechococcus, ultra- and nanophytoplankton, cryptophytes, and coccolithophores were enumerated by flow cytometry. The abundance of bacteria was well correlated with the concentration of SRP, and that of the ultra- and nanophytoplankton was well correlated with the concentration of N+N. The only group whose concentration was correlated with temperature was Prochlorococcus, and its abundance was unrelated to the concentrations of nutrients measured at the surface.We combined our transect results with time-series measurements from the BATS site and data from select depth profiles, and contrasted these North Atlantic data sets with time-series of N and P nutrient measurements from a station in the North Pacific subtropical gyre near Hawaii [Hawaii Ocean Time-series (HOT) site]. Two prominent differences are readily observed from this comparison. The [N+N] : [SRP] molar ratios are much less than 16 : 1 during stratified periods in surface waters at the BATS site, as is the case at the HOT site year round. However, following deep winter mixing, this ratio is much higher than 16 : 1 at BATS. Also, SRP concentrations in the upper 100 m at BATS fall in the range 1–10 nM during stratified periods, which is at least one order of magnitude lower than at the HOT site. That two ecosystems with comparable rates of primary and export production would differ so dramatically in their nutrient dynamics is intriguing, and highlights the need for detailed cross ecosystem comparisons.     

Comparison of time-dependent extended mild-slope equations for random waves

The extended mild-slope equations of Suh et al. [Suh, K.D., Lee, C., Park, W.S., 1997. Time-dependent equations for wave propagation on rapidly varying topography. Coastal Eng., 32, 91–117] and Lee et al. [Lee, C., Kim, G., Suh, K.D., 2003. Extended mild-slope equation for random waves. Coastal Eng., 48, 277–287] are compared analytically and numerically to determine their applicability to random wave transformation. The geometric optics approach is used to compare the two models analytically. In the model of Suh et al., the wave number of the component wave with a local angular frequency ω is approximated with an accuracy of O(ω − ω¯) at a constant water depth, where ω¯ is the carrier frequency of random waves. In the model of Suh et al., however, the diffraction effects and higher-order bottom effects are considered only for monochromatic waves, and the shoaling coefficient of random waves is not accurately approximated. This inaccuracy arises because the model of Suh et al. was derived for regular waves. In the model of Lee et al., all the parameters of random waves such as wave number, shoaling coefficient, diffraction effects, and higher-order bottom effects are approximated with an accuracy of O(ω − ω¯). This approximation is because the model of Lee et al. was developed using the Taylor series expansion technique for random waves. The result of dispersion relation analysis suggests the use of the peak and weighted-average frequencies as a carrier frequency for Suh et al. and Lee et al. models, respectively. All the analytical results are verified by numerical experiments of shoaling of random waves over a slightly inclined bed and diffraction of random waves through a breakwater gap on a flat bottom.     

YREE sorption on hydrous ferric oxide in 0.5 M NaCl solutions: A model extension

Distribution coefficients, _iK_Fe, were measured for sorption of yttrium and the rare earth elements (YREEs) on hydrous ferric oxide (HFO) in 0.5 M NaCl solutions over the pH range 3.9–8.4 (T = 25 °C). An existing, non-electrostatic model [Quinn, K.A., Byrne, R.H., Schijf, J., 2006. Sorption of yttrium and rare earth elements by amorphous ferric hydroxide: influence of pH and ionic strength. Mar. Chem. 99, 128–150] was modified to account for sorption of YREE–chloride complexes, as well as YREE–hydroxide complexes at elevated pH. The extended model, which allows calculation of _iK_Fe as a function of [H⁺], contains two parameters, _SK₁ and _SK₂, to describe the equilibrium between positive, neutral, and negative forms of the hydroxyl functional groups on the HFO surface. In addition, it contains several composite, conditional stability constants, A_n, that represent YREE bonding to the neutral groups with release of n protons and/or to the negatively charged groups with release of n ? 1 protons.In 0.5 M NaCl solutions, YREE sorption on HFO is weaker and less pH dependent, yielding only 0.7–0.9 protons per YREE cation on average, vs. about 1.5 at low ionic strength. This is due to enhanced deprotonation of the HFO surface (_SK₁ ~ 0, p_SK₂ = 6.16), leading to an increase in the proportion of negatively charged groups, which release fewer protons per YREE cation sorbed. On a logarithmic scale, _iK_Fe is a nearly linear function of pH, except at pH > 8 where cumulative sorption of YREE–hydroxide complexes causes it to rise more rapidly, especially for the heavy REEs. Both our own data and prior results from the literature are well described by the extended model, using only three adjustable parameters, A₁–A₃. The constant A₃, representing YREE bonding to the negatively charged groups with release of two protons, shows an excellent linear free-energy relation when plotted against the first YREE hydrolysis constant, β₁*. There is no evidence for YREE bonding to the positively charged groups (i.e., A₀ = 0).     

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.     

Simulation of turning circle by CFD: Analysis of different propeller models and their effect on manoeuvring prediction

Propeller modelling in CFD simulations is a key issue for the correct prediction of hull-propeller interactions, manoeuvring characteristics and the flow field in the stern region of a marine vehicle. From this point of view, actuator disk approaches have proved their reliability and computational efficiency; for these reasons, they are commonly used for the analysis of propulsive performance of a ship. Nevertheless, these models often neglect peculiar physical phenomena which characterise the operating propeller in off-design condition, namely the in-plane loads that are of paramount importance when considering non-standard or unusual propeller/rudder arrangements. In order to emphasize the importance of these components (in particular the propeller lateral force) and the need of a detailed propeller model for the correct prediction of the manoeuvring qualities of a ship, the turning circle manoeuvre of a self-propelled fully appended twin screw tanker-like ship model with a single rudder is simulated by the unsteady RANS solver χnavis developed at CNR-INSEAN; several propeller models able to include the effect of the strong oblique flow component encountered during a manoeuvre have been considered and compared. It is emphasized that, despite these models account for very complex and fundamental physical effects, which would be lost by a traditional actuator disk approach, the increase in computational resources is almost negligible. The accuracy of these models is assessed by comparison with experimental data from free running tests. The main features of the flow field, with particular attention to the vortical structures detached from the hull are presented as well.     

Determining the weights of two types of artificial reefs required to resist wave action in different water depths and bottom slopes

The interaction between waves and artificial reefs (ARs; a hollow cube weighing 8.24 kN (0.84 t) and a water pipe weighing 1.27 kN (0.13 t)) in shallow waters was investigated with respect to variations in design weight, orientation (for cube; 45° and 90° angles, for pipe; 0°, 90°, and 180° angles to flow), depth (1–20 m), and bottom slope (10^?1, 30^?1, and 50^?1). Physics equations and FLUENT software were used to estimate resisting and mobilising forces, and drag coefficients. Drag coefficients for the hollow cube were 0.76 and 0.85 at 45° and 90° angles to the current, respectively, and 0.97, 0.38, and 1.42 for the water pipe at 0°, 90°, and 180° angles to the current, respectively. Deepwater offshore wave conditions at six stations were transformed into shallow nearshore waters representative of the artificial reef site. Waters deeper than 12 and 16 m are safe to deploy blocks with angles of 45° and 90°, respectively. However, water pipes constructed at angles of 90° and 180° to the current were estimated as being unstable for 365 out of 720 cases at all stations (only one station was stable for all cases). Water pipes angled at 0° were found to be stable in all 360 cases. Slope had a significant effect on weight and depth. Results from this study provide an important reference for engineers performing projects aiming to increase the performance and service life of ARs.     

Effects of benzo[a]pyrene on DNA damage and histological alterations in gonad of scallop Chlamys farreri

To investigate the biological impact of polycyclic aromatic hydrocarbons (PAHs) on reproductive system, scallops Chlamys farreri were continuously exposed to benzo[a]pyrene (BaP) (0.5, 3, 10 μg L^?1) during 15 days. DNA damage and histological alterations were examined in female gonad. DNA strand break levels significantly increased after 12 h exposure, and remained high and significantly different from control values until the end of the exposure. In the ovaries of the scallops exposed to 10 μg L^?1 BaP for ten days, histological analysis showed that the cytoplasts of the oocytes in the outer layer of the ovaries became sparse, and the nuclear membranes were obscure. Damaging effects on ovaries and oocytes were more severe after 15 days exposure. Degenerating oocytes increased and the connective tissue of the ovary envelops became loose. Electron microscopic examination revealed ultrastructural aspects of degenerating oocyte and degenerated oocyte after 15 days exposure.     

Physical drivers of phytoplankton production in the southern Benguela upwelling system

Investigations of primary production (PP) were undertaken in the southern Benguela ecosystem during two research surveys in October 2006 and May 2007. Significant differences in environmental conditions, as well as biomass and PP, were observed between October and May. During October, integrated biomass and PP were significantly higher, ranging from 20.43 to 355.01 mg m⁻², and 0.71 to 6.98 g C m⁻² d⁻¹, respectively, than in May, where the range was 47.92–141.79 mg m⁻², and 0.70–3.35 g C m⁻² d⁻¹, respectively. Distribution patterns indicated low biomass and PP in newly upwelled water along the coast, higher biomass and PP in the mid-shelf region, while lower values were observed at and beyond the shelf edge. Latitudinal variations showed consistently higher biomass and PP in the St. Helena Bay region compared to biomass and PP south of Cape Town. During both surveys, phytoplankton communities were comprised primarily of diatoms and small flagellates, with no significant differences. Phytoplankton adaptation to environmental variability was characterised by increased P_m^B and E_k under elevated temperatures and irradiance, while no clear relationships were evident for α^B. Generalised Additive Models (GAMs) showed that photosynthetic parameters were all significant predictors of photosynthesis rates (P_z), with P_m^B being the most important, accounting for 36.97% of the deviance in P_z. However, biomass levels and environmental conditions exerted a much greater influence on P_z, with irradiance explaining the largest proportion (68.24%) of the deviance. Multiple predictor GAMs revealed that 96.26% of the deviance in P_z could be explained by a model which included nitrate, chlorophyll a, and irradiance.     

Effect of waves on cavitation and pressure pulses of a tanker with twin podded propulsion

There is increasing interest in optimizing ships for the actual operating condition rather than just for calm water. In order to optimize the propeller designs for operations in waves, it is essential to study how the propeller performance is affected by operation in waves. The effect of various factors that influence the propeller is quantified in this paper using a 8000 dwt chemical tanker equipped with twin-podded propulsion as a case vessel. Propeller performance in waves in terms of cavitation, pressure pulses, and efficiency is compared with the performance in calm water. The influence of wake variation, ship motions, RPM fluctuations and speed loss is studied. Substantial increase in cavitation and pressure pulses due to wake variation in the presence of waves is found. It is found that the effect of other factors is relatively small and easier to take into account as compared to wake variation. Therefore, considering the wake variation at least in the critical wave condition (where the wavelength is close to ship length) in addition to calm water wake is recommended in order to ensure that the optimized propeller performs well both in calm water and in waves.     

Focused wave evolution using linear and second order wavemaker theory

In this paper, the evolution of focused waves using different paddle displacements (piston type) under laboratory conditions is presented. It is well known that in intermediate water depths, linear paddle displacements will generate spurious, free, sub and super harmonics. Thus, a second order correction to suppress these spurious free sub and super harmonics was used to generate the focused waves. The focused waves were generated in the laboratory using a linear superimposition principle, in which the wave paddle displacement is derived based on the sum of a number of sinusoidal components at discrete frequencies, whose phases are accordingly set to focus at a particular location. For this method of generation, the second order wave maker theory proposed by Schäffer [24] can be easily adopted and was used in the present study. Two different centre frequencies (f_c = 0.68 Hz and 1.08 Hz) with three different bandwidth ratios (Δf/f_c = 0.5, 0.75 and 1.0) were tested in a constant water depth, to consider both narrow and broadband spectra. These test cases correspond to wave focusing packets propagating in intermediate and deep water regions. Further, for each wave packet, two different amplitudes were considered in order to analyze non-breaking and breaking cases. Thus, by systematically generating the wave packets using the linear and second order paddle displacements, the analysis was carried out for the spectral and temporal evolution of selected long waves. The temporal evolution of the selected harmonics was analyzed using the Inverse Fast Fourier Transform (IFFT), to show the propagation of the spurious, free, long waves. Further, the variations in energy for the lower, higher and primary frequency ranges are reported for different wave paddle displacements. The analysis revealed that for the broadband spectrum the differences are more pronounced when using linear paddle displacements. We have also noticed a shift in focusing/breaking location and time (i.e. premature) due to the increase in crest height using linear displacements. The experiment data used in this paper has been provided as a supplementary, which can be used to validate the numerical models.     

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.