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1.
A series of flow induced vibration (FIV) experiments for an equilateral triangle prism elastically mounted in a water channel are performed with different system stiffness at constant damping and mass. An amplitude variation coefficient is proposed to describe FIV stationarity in the present study. The FIV of the prism can be divided into three primary regions based on the amplitude and frequency responses, which are the vortex induced vibration (VIV) branch, the transition branch from VIV to galloping, and the galloping branch. The transition branch occurs at the reduced velocity in the range of 7.8 < Ur = U/(fn,air·D) < 10.4, accompanied with a relatively rapid increase in amplitude and a precipitous drop in frequency and vibration stationarity. In addition, the reduced velocity where the transition region is initiated is independent of the system stiffness. The maximum amplitude reaches 3.17 D in the galloping branch. The ratio of the response frequency to the natural frequency of the prism in air remains locked to approximately 0.65 throughout the fully developed galloping branch. Large amplitude responses in an infinite range of flow velocities, excellent vibration stationarity and steady vibration frequencies, which are characteristics of the galloping of the prism, have a positive impact on improving energy conversion.  相似文献   

2.
The venerid clam Ruditapes philippinarum is the most prominent suspension-feeding bivalve inhabiting muddy intertidal seagrass beds in Arcachon Bay (SW France). It is exploited by fishermen, and Arcachon Bay ranks number one in France in terms of production and total biomass of this species. Previous studies revealed a decrease in the standing stock of R. philippinarum since 2003 and unbalanced length–frequency distributions with a lack of juveniles and of adults > 40 mm. Consequently, the population dynamics of this bivalve were studied at four intertidal sites and one oceanic site in Arcachon Bay. As clam size structure did not allow classical dynamics computations, field monitoring was coupled with field experiments (tagging–recapture) over two years. Monitoring of condition index and gonadal maturation stages highlighted a high variability in spawning number and intensity between sites. Recruitment events in the exploited area varied spatially but with uniformly low values. Von Bertalanffy Growth Function (VBGF) parameters (K, L∞) were determined using Appeldoorn and ELEFAN methods. In the exploited sites in the inner lagoon, K was relatively high (mean = 0.72 yr? 1) but L∞ was low (mean = 41.1 mm) resulting in a moderate growth performance index (Φ′ = 2.99). Growth parameters were not correlated with immersion time and L∞ was different between sites. Comparison of mortality coefficients (Z) between cage experiments and field monitoring suggested that fishing accounts for 65–75% of total adult mortality. Low recruitment, a low growth rate and a normal mortality rate led to low somatic production (4.1 and 8.7 g Shell-Free Dry Weight (SFDW) m? 2 yr? 1) and an annual P/B ratio from 0.44 to 0.92 yr? 1. Under current conditions, the possibility of a sustainable population in Arcachon Bay will strongly depend on recruitment success and fishing management.  相似文献   

3.
《Coastal Engineering》2006,53(11):929-945
A finite difference model based on a recently derived highly-accurate Boussinesq-type formulation is presented. Up to the third-order space derivatives in terms of the velocity variables are retained, and the horizontal velocity variables are re-formulated in terms of a velocity potential. This decreases the total number of unknowns in two horizontal dimensions from seven to five, simplifying the implementation, and leading to increased computational efficiency. Analysis of the embedded properties demonstrates that the resulting model has applications with errors of 2 to 3% for (wavenumber times depth) kh ≤ 10 in terms of dispersion and kh ≤ 4 in terms of internal kinematics. The stability and accuracy of the discrete linearised systems are also analysed for both potential and velocity formulations and the advantages and disadvantages of each are discussed. The velocity potential model is then used to study physically demanding problems involving highly nonlinear wave run-up on a bottom-mounted (surface-piercing) plate. New cases involving oblique incidence are considered. In all cases, comparisons with recent physical experiments demonstrate good quantitative accuracy, even in the most demanding cases, where the local wave steepness can exceed (waveheight divided by wavelength) H / L = 0.20. The velocity potential model is additionally shown to have numerical advantages when dealing with wave–structure interactions, requiring less smoothing around exterior structural corners.  相似文献   

4.
An intra-annual investigation of the fugacity of CO2 (fCO2) has been conducted in surface waters of the north-eastern shelf of the Gulf of Cádiz (SW Iberian Peninsula) in four cruises made in 2006 and 2007. Intra-annual variability of fCO2 was assessed and is discussed in terms of mixing, temperature and biology. In the study area of the shelf, thermodynamic control over fCO2 predominates from early May to late November, and this is opposite and similar in magnitude to the net biological effect. However, biological control over fCO2 predominates during winter. The results suggest that surface waters in the coastal area are under-saturated with respect to atmospheric CO2 during most of the year; therefore they represent a sink for atmospheric CO2 between November and May (? 1.0 mmol m? 2 day? 1), but a weak source in June (1.3 mmol m? 2 day? 1). In contrast, the coastal ecosystems studied (the lower estuary of Guadalquivir Estuary and Bay of Cádiz) acted as a weak sink for atmospheric CO2 during February (? 1.3 mmol m? 2 day? 1) and as a source between May and November (2.6 mmol m? 2 day? 1). The resulting mean annual CO2 flux in the north-eastern shelf of the Gulf of Cádiz was ? 0.07 mol m? 2 year? 1 (? 0.2 mmol m? 2 day? 1), indicating that the area acts as a net sink on an annual basis.  相似文献   

5.
The wave transmission, reflection, and energy dissipation of the double rows of vertical piles suspending horizontal steel C shaped bars are experimentally and theoretically studied under normal regular waves. Different wave and structural parameters are investigated e.g. the wave length, the C shaped bars draft and spacing, the supporting piles diameter and spacing, and the space between the double rows. Also, the theoretical model based on an eigenfunction expansion method is developed to study the hydrodynamic breakwater performance. In order to examine the validity of the theoretical model, the theoretical results are compared with the experimental and theoretical results obtained by different authors. Comparison between experiments and predictions showed that theoretical model provides a good estimate to the different hydrodynamic coefficients when the friction factors of the upper and the lower parts are fU = 1.5 and fL = 0.75. The present breakwater physical model gives efficiency near other similar systems of different shapes.  相似文献   

6.
Air–sea gas transfer velocities are estimated for one year using a 1-D upper-ocean model (GOTM) and a modified version of the NOAA–COARE transfer velocity parameterization. Tuning parameters are evaluated with the aim of bringing the physically based NOAA–COARE parameterization in line with current estimates, based on simple wind-speed dependent models derived from bomb-radiocarbon inventories and deliberate tracer release experiments. We suggest that A = 1.3 and B = 1.0, for the sub-layer scaling parameter and the bubble mediated exchange, respectively, are consistent with the global average CO2 transfer velocity k. Using these parameters and a simple 2nd order polynomial approximation, with respect to wind speed, we estimate a global annual average k for CO2 of 16.4 ± 5.6 cm h?1 when using global mean winds of 6.89 m s?1 from the NCEP/NCAR Reanalysis 1 1954–2000. The tuned model can be used to predict the transfer velocity of any gas, with appropriate treatment of the dependence on molecular properties including the strong solubility dependence of bubble-mediated transfer. For example, an initial estimate of the global average transfer velocity of DMS (a relatively soluble gas) is only 11.9 cm h?1 whilst for less soluble methane the estimate is 18.0 cm h?1.  相似文献   

7.
《Ocean Modelling》2009,26(3-4):154-171
Ocean surface mixing and drift are influenced by the mixed layer depth, buoyancy fluxes and currents below the mixed layer. Drift and mixing are also functions of the surface Stokes drift Uss, volume Stokes transport TS, a wave breaking height scale Hswg, and the flux of energy from waves to ocean turbulence Φoc. Here we describe a global database of these parameters, estimated from a well-validated numerical wave model, that uses traditional forms of the wave generation and dissipation parameterizations, and covers the years 2003–2007. Compared to previous studies, the present work has the advantage of being consistent with the known physical processes that regulate the wave field and the air–sea fluxes, and also consistent with a very large number of in situ and satellite observations of wave parameters. Consequently, some of our estimates differ significantly from previous estimates. In particular, we find that the mean global integral of Φoc is 68 TW, and the yearly mean value of TS is typically 10–30% of the Ekman transport, except in well-defined regions where it can reach 60%. We also have refined our previous estimates of Uss by using a better treatment of the high frequency part of the wave spectrum. In the open ocean, Uss ≃ 0.013U10, where U10 is the wind speed at 10 m height.  相似文献   

8.
Experiments employing a low-mass-damping cylinder have been conducted to determine the vortex-induced vibration (VIV) response of four suppressors of the flexible-shroud family. The VIV suppressors were inspired in the concept of the Ventilated Trousers (VT), a flexible shroud composed of a flexible net fitted with three-dimensional bobbins. Reynolds number varied between 5 × 103 and 25 × 103, while reduced velocity varied from 2 to 26. The VIV dynamic response showed that the VT suppressed the peak amplitude of vibration down to 40% of that of a bare cylinder. Other flexible shrouds also achieved suppression, but not as efficiently. Drag was reduced during the VIV synchronization range, but remained above the value for a bare static cylinder thereafter. Spectral analysis of displacement and lift revealed that, depending on the geometry and distribution of the bobbins, the flexible shroud can develop an unstable behavior, capturing energy from the wake and sustaining vibrations for higher reduced velocities. PIV measurements of the wake revealed that the entrainment flow through the mesh is necessary to extend the vortex-formation length of the wake; this mechanism only occurs for the VT mesh.  相似文献   

9.
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.  相似文献   

10.
Cockle (Cerastoderma edule) population dynamics were studied at the southern limit of the distribution of this marine bivalve in Merja Zerga, Morocco. Parameters such as growth, mortality, and production were compared with those of a population at Arcachon Bay (France) a site in the center of the cockle's range. At each sampling period between two and three cohorts were simultaneously observed at each site and the average total abundance was usually higher at Merja Zerga. Recruitment occurred at both sites in spring when temperature rose above 19 °C, independently of the month. In Merja Zerga, winter recruitment was also observed at one occasion, following high sediment disturbance. The first year (2005–06) at Merja Zerga, the mortality rate was close to nil for juveniles and was Z = 1.5 yr? 1 for adults, providing a high production (64 g dry weight m? 2 yr? 1). At Arcachon during the same period, the juvenile mortality rate was Z = 10.9 yr? 1, the adult mortality rate was 3.4 yr? 1 and production was 26 gDW m?2 yr? 1. The second year (2006–07), mortality after recruitment was much higher (Z = 8.6 yr? 1, for juveniles) and similar to what was observed at Arcachon (Z = 8.4 yr? 1). Mortality rate of adults was higher at Merja Zerga (Z = 3.0 yr? 1) than at Arcachon (Z = 1.5 yr? 1). Production was lower at Arcachon than at Merja Zerga although growth performances were higher at Arcachon. The higher growth performance at Arcachon (Φ′ = 3.3) was mainly due to high asymptotic length (L∞ = 38 mm) and was related to low intraspecific competition compared to Merja Zerga where cockle abundance was higher (Φ′ = 3.1, L∞ = 31 mm). P/B was low in both sites and slightly higher at Arcachon (1.1–1.5 against 1.0–1.1 yr? 1). At Arcachon, recruitment was correlated with temperature, a peak occurring when temperature rose above 19 °C (June–July). At Merja Zerga, recruitment was already 2–3 months earlier but was not significantly correlated to temperature.This study showed that population dynamics of cockles at the southern limit of this distribution fell in the range of what was observed elsewhere in the North-Eastern Atlantic coast. Most factors that were involved in population regulation (intraspecific competition, predation and sediment dynamics) were not strictly dependent on latitude. The direct role of temperature (latitude dependent factor) was not obvious. Variation in temperature could explain the recruitment delay between Arcachon and Merja Zerga and the low maximum shell length at Merja Zerga.  相似文献   

11.
The aim of this paper is to evaluate the accuracy, stability and efficiency of the overset grid approach coupled with the RANS (Reynolds Averaged Navier-Stokes) model via the benchmark computations of flows around a stationary smooth circular cylinder. Two dimensional numerical results are presented within a wide range of Reynolds numbers (6.31 × 104 ∼ 7.57 × 105) including the critical flow regime. All the simulations are carried out using the RANS solver pimpleFoam provided by OpenFOAM, an open source CFD (Computational Fluid Dynamics) toolkit. Firstly, a grid convergence study is performed. The results of the time-averaged drag and lift force coefficients, root-mean square value of lift force coefficient and Strouhal number (St number) are then compared with the experimental data. The velocity, vorticity fields and pressure distribution are also given. One main conclusion is that the numerical solutions in regard to a fixed cylinderare not deteriorated due to the implementation of the overset grid. Furthermore, it can be an appealing approach to facilitate simulations of Vortex Induced Vibrations (VIV), which involves grid deformation. The present study is a good start to implement the overset grid to solve VIV problems in the future.  相似文献   

12.
《Coastal Engineering》2006,53(5-6):531-542
The inception of the sheet flow regime as well as the effects of the phase lag when the sheet flow regime is established were investigated for oscillatory flows and combined steady and oscillatory flows. A new criterion for the inception of sheet flow is proposed based on around 300 oscillatory flow cases from experiments. This criterion was introduced in the Camenen and Larson [Camenen, B., Larson, M., 2005. A bedload sediment transport formula for the nearshore. Estuarine, Coastal and Shelf Science 63, 249–260.] bed load formula in order to take into account phase-lag effects in the sheet flow regime. The modification of the Camenen and Larson formula significantly improves the overall agreement with data and yields a correct behavior in relation to some of the main governing parameters, which are the median grain size d50, the orbital wave velocity Uw, and the wave period Tw. The calibration of the new formula was based on more than 200 experimental data values on the net sediment transport rate for a full wave cycle. A conceptual model was also proposed to estimate the ratio between sediment transport rate with and without phase lag, (rpl = qs,net / qs,net,ϕ=0). This simple model provides accurate results and may be used together with any quasi-steady model for bed load transport.  相似文献   

13.
Diagenetic analysis based on field and petrographic observations, isotope and microthermometric data was used to reconstruct the fluid flow history of the Cretaceous shallow water limestones from the Panormide platform exposed in north-central Sicily. Analysis focused on diagenetic products in cavities and dissolution enlarged fractures of the karstified limestones that occur just below a regional unconformity. The fluid flow history could be broken down into five stages that were linked to the kinematic and burial history of the region. (1) Petrography (zoned cathodoluminescence and speleothem textures) and stable isotopes (6.5 < δ18OV-PDB < ?3.5‰ and 0 < δ13CV-PDB < ?14‰) indicate that the earliest calcite phase was associated with karstification during emergence of the platform. Limestone dissolution at this stage is important with regard to possible reservoir creation in the Panormide palaeogeographic domain. (2) Fine-grained micrite sedimentation, dated as latest Cretaceous by nannopalaeontology and its 87Sr/86Sr isotope ratio (0.7078), marks replacement by marine fluids during subsequent submergence of the karstified platform. (3) The following calcite cement was still precipitated by marine-derived fluids (?7.0 < δ18OV-PDB < ?5.0‰ and ?3.0 < δ13CV-PDB < 0.5‰/Tm = ?2 to ?5 °C), but at increasingly higher temperatures (Th = 60–120 °C). This has been interpreted as precipitation during Oligocene foredeep burial. (4) Hot (Th = 130–180 °C), low saline (Tm < ?2.5 °C) fluids with increasingly higher calculated δ18OSMOW signatures (+6 to +14‰) subsequently invaded the karst system. These fluids most likely migrated during fold and thrust belt development. The low salinity and relatively high δ18OSMOW signatures of the fluids are interpreted to be the result of clay dewatering reactions. The presence of bitumen and associated fluorite with hydrocarbon inclusions at this stage in the paragenesis constrains the timing of oil migration in the region. (5) Finally, high saline fluids with elevated 87Sr/86Sr (0.7095–0.7105) signatures invaded the karst system. This last fluid flow event was possibly coeval with localized dolomitization and calcite cementation along high-angle faults of Pliocene age, as suggested by identical radiogenic signatures of these diagenetic products.  相似文献   

14.
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.  相似文献   

15.
We have employed laboratory and numerical experiments in order to investigate propagation of waves in both long and short-crested wave fields in deep water. For long-crested waves with steepness, ϵ = kcac = 0.1 (a fairly extreme case), reliable prediction can be performed with the modified nonlinear Schrödinger equation up to about 40 characteristic wavelengths. For short-crested waves the accuracy of prediction is strongly reduced with increasing directional spread.  相似文献   

16.
Sterol and alkenone compositions in suspended particle and surface sediment samples collected in the Northwestern Mediterranean Sea during the MEDFLUX program were used to evaluate the relative importance of biotic and abiotic degradation processes on marine organic matter. Alkenone concentrations decreased much more rapidly (~ 500 fold) between 5 and 800 m than Δ5-sterols (~ 100-fold) or POC (~ 100-fold). The diverse functional groups attached to the stable tetracyclic carbon skeleton of Δ5-sterols appeared to be useful for estimating the relative effects of biotic vs. abiotic (photooxidation and autoxidation) degradation. Products of abiotic degradation predominated over products of biotic degradation in suspended particles in the NW Mediterranean. For alkenones, the U37K′ index increased from 0.43 to 0.55 with increasing water depth, and a good correlation between variations of U37K′ and concentrations of specific Δ5-sterol autoxidation products points to selective autoxidation of alkenones in suspended particles. Stereomutated alkenones (with cis double bonds) were detected in the surface sediment, allowing us to estimate that stereomutation resulted in a + 0.05 increase in U37K′. Therefore, abiotic degradation may be another factor effect on alkenone-derived paleothermometry.  相似文献   

17.
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 PW = 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 PG = 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.  相似文献   

18.
The paper examines the dependency between total sediment transport, q, and grain size, D (i.e. q ∝ Dp) under dam break generated swash flows. Experiments were performed in a dam break flume over a sloping mobile sand bed with median grain sizes ranging from 0.22 mm to 2.65 mm. The total sediment transport was measured by truncating the flume bed and collecting the sediment transported over the edge. The experiments were designed to exclude pre-generated turbulence and pre-suspended sediment so as to focus solely on the swash flow. The magnitude and nature of the grain size dependency (i.e. p value) were inferred for different flow parameters; the initial dam depth, do, the integrated depth averaged velocity cubed, ∫ u3dt, and against the predicted transport potential, qp, using the Meyer-Peter Muller (MPM) transport model and variations of that model. The data show that negative dependencies (p < 0) are obtained for do and qp, whilst positive dependencies (p > 0) are obtained for ∫ u3dt. This indicates that a given do and qp transport less sediment as grain size increases, whereas transport increases with grain size for a given ∫ u3dt. The p value is found to be narrowly ranged, 0.5 ≤ p ≤ − 0.5. On average, the incorporation of a pressure gradient term via the piezometric head into the MPM formulation reduces qp by 4% (fine sand) to 18% (coarse sand). The measured total transport for fine and coarse sands is best predicted using MPM and MPM + dp*/dx respectively. However, the inferred optimum transport coefficient in the MPM formulation is about 30, much higher than the standard coefficient in a steady flow and this is not due to the presence of the pre-suspended sediment. The optimum transport coefficient indicates some sensitivity to grain size, suggesting that some transport processes remain unaccounted for in the model.  相似文献   

19.
We investigated a year-long (September 1992 to August 1993) time series of total mass, calcium carbonate, organic carbon, opal, and alkenone fluxes in sinking particles collected with sediment traps moored at 1770 and 4220 m in the central equatorial Pacific. The total mass fluxes varied from 14.7 to 68.7 mg/m2/day at 1770 m, with greater fluxes in October–November and February–April, and from 14.6 to 50.4 mg/m2/day with peak fluxes during October–November at 4220 m. High flux in the spring season shown at 1770 m was not indicated at 4220 m; instead, a slight increase was shown during a broad period from March to June. The calcium carbonate fluxes varied from 10.8 to 49.1 mg/m2/day with higher fluxes in October–November and March–April at 1770 m, and from 8.9 to 37.0 mg/m2/day with a higher flux in October–November at 4220 m. The organic carbon fluxes varied from 0.36 to 5.91 mg/m2/day, with higher fluxes in October–November and March–April at 1770 m, and from 0.72 to 2.58 mg/m2/day at 4220 m. The annual mean organic carbon flux was 1.84 and 1.28 mg/m2/day at 1770 and at 4220 m, respectively. These values were less than half of those reported for the EqPac sediment trap experiment. The opal fluxes varied from 0.55 to 4.4 mg/m2/day at 1770 m and from 1.23 to 2.95 mg/m2/day at 4220 m. Alkenone fluxes varied significantly from 0.05 to 0.84 μg/m2/day, with high values in November, February–March, and June at 1770 m. For the 4220 m trap, these values ranged from 0.05 to 0.25 μg/m2/day, with slightly higher fluxes in April–May and June–July, which followed periods of high alkenone fluxes observed in February–April and June–July, respectively, at 1770 m depth. These values were remarkably low compared with those reported by the previous studies at other sites. U37K′ values were constantly high >0.95 throughout the collection period. However, relatively low U37K′ values (0.92 and 0.93) were occasionally observed during February to March. Estimated alkenone temperatures from those U37K′ values were about 27–29°C and consistent with the observed temperature of the upper layer at ca.100 m depth. The seasonal change of the U37K′ values could be affected by not only water temperature but also the relative amount of ‘warm’ and ‘cold’ types of alkenone producer in the central equatorial Pacific.  相似文献   

20.
《Marine Chemistry》2007,103(1-2):30-45
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 1011.1 and 1011.9. 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 kd = 1.5 × 10− 3–17 × 10− 2 s− 1 and kf = 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 (βFe(TAC)2′) varied between 22 and 23.4 for S = 10 and S = 26 more or less equal to that known from the literature (logβFe(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 logβFe(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 βFe(TAC)2′ is known.  相似文献   

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