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1.
A field investigation was carried out to collect data of inner bar migration. Profiles were measured once or twice a week for a two-year period at Naka Beach, Ibaraki Prefecture, Japan. It was found that the onshore migration of inner bars could be described by two dimensionless quantities as: 5D(Hb)max < (Hb)maxgT2max < 20D(Hb)max where (Hb)max is the maximum value of daily average breaker height during one interval between surveys, Tmax is the average wave period of the day giving (Hb)max, D is the mean size of the beach sediment, and g is the acceleration due to gravity. Analyses based on surfzone sediment dynamics yields v?(wDb) = 2 × 10?11 ((H?bD)3, where v? is the average speed of onshore bar-migration, b is the bar height, H?b is the average breaker height, and w is the fall velocity of the beach sediment. Nomographs for the speed of landward migrating bars are also presented.  相似文献   

2.
Velocity and suspension measurements in the logarithmic layer of hydraulically smooth turbulent tidal flow from the North Sea are reported. The data were not compatible with the assumption of Newtonian flow for the experimental seawater—clay suspension.Laboratory measurements were initiated with mud and seawater from the North Sea in which the boundary-layer structure of this two-phase flow was measured down into the viscous sublayer. The dilute seawater—clay suspension was a mixture of illite, kaolinite and chlorite minerals with concentrations less than 380 mg/l and exhibited turbulent drag reduction.By reviewing flow measurements of other authors it is suggested that turbulent drag reduction occurs on a geophysical scale if the flows transport cohesive sediments. It is proposed that drag reduction is caused by dynamic interaction between turbulent shear strain in the flow and deformation of aggregates.As a consequence, the values of the critical friction velocity u1 crit and of erosion rates must be reviewed for cohesive bottom materials. Normally they were obtained under the assumption of a Newtonian flow structure which is not applicable if the flow transports cohesive sediments.To detect the occurrence of drag reduction in geophysical boundary layers (hydraulically smooth), flow measurements must be performed down into the viscous sublayer. The adequate velocity sensors must have a diameter of ?1 mm.  相似文献   

3.
The apparent ionization constants for silicic acid, k1 and k2, and the ionic product of water, kw, have been determined in 0.05, 0.1, 0.2, 0.4 and 2.0 M Na(CI) media at 25°C. The medium dependence of these constants was found to fit equations of the form
logki=logKi+aiI12(1+I12)+biI
where K1 is the ionization constant in pure water, αi and bi are parameters of which bi has been adjusted to present data. The following results were obtained (αi, bi): pK1 = 9.84, (1.022, ?0.11); pK2 = 13.43, (2.044, ?0.20); and pKw = 14.01 (1.022, ?0.22). ki values are collected in Tables I and II. Attempts have been made to explain the medium dependence of k1 and k2 with weak sodium silicate complexing according to the equilibria
Na++SiO(OH)?3?NaSiO(OH)3;k11
Na++SiO2(OH)22?NaSiO2(HO)?2; k21
giving k11 = 0.37M?1 and k21= 3.0M?1. However, these weak interactions cannot be interpreted unambiguously from potentiometric data at different 1-levels. Probably the medium dependence could equally well be expressed by variations in the activity coefficients.The measurements were performed as potentiometric titrations using a hydrogen electrode. The average number of OH- reacted per Si(OH)4, Z, has been varied within the limits 0 ? Z ? 1.1 and B1, the total concentration of Si(OH)4, between 0.001 M and 0.008 M. k1 was evaluated from experimental data with B ? 0.003 M, and k2 with B ? 0.008 M and Z ? 0.95.  相似文献   

4.
An investigation of ferric ion complexing has been conducted in synthetic media and seawater at 25°C. Formation constants were potentiometrically determined for the species FeCl2+, FeCl2+, FeOH2+, and Fe(OH)2+ at an ionic strength of 0.68 m. Formation constants for the ferric chloride complexes were determined as Clβ1 = 2.76 and Clβ2 = 0.44. In a study of the reaction Fe3+ + nH2O ? Fe(OH)n(3?n)+ + nH+ in NaClO4, NaNO3 and NaCl the formation constants 1β1and1β2 were shown to be relatively independent of medium when the effects of nitrate and chloride complexing were taken into account. The average values obtained for these constants are 1β1 = 1.93 · 10?3and1β2 = 8.6 · 10?8. Reasonable agreement with these values was obtained when these constants were determined in seawater by accounting for the effects of chloride, fluoride and sulfate complexing.  相似文献   

5.
The density of artificial seawater has been measured with a magnetic float densitometer at 1 atm. from 0 to 40°C (in 5° intervals) and from 0 to 21‰ chlorinity. The densities at each temperature have been fitted to a modified Root (1933) equation, d = d0 + AV′ ClV + BV′ ClV32 and an equation based on the Debye-Hückel limiting law, d = d0 + AV ClV + BV ClV32 + CV ClV2 where AV′, BV′, AV, BV and CV are temperature-dependent constants (related to the ion-water and ion-ion interactions of the major components), d0 is the density of pure water and ClV is the volume chlorinity — ClV = Cl (‰) × density. The densities fit these equations to ±9 p.p.m. from 0 to 25°C and ±18 p.p.m. from 30 to 40°C. The densities for artificial seawater are in good agreement with our measurements of Copenhagen seawater and the results for natural seawater obtained from Knudsen's tables.The expansibilities of the artificial seawater mixtures have been calculated from the temperature dependence of the densities. The resulting expansibilities at each temperature were fitted to the equations α = α0 + AE′ ClV + BE′ ClV32 and α = α0 + AE ClV + BE ClV32 + CE ClV2 where AE′, BE′, AE, BE and CE are constants (related to the effect of temperature on the ion-water and ion-ion interactions of the major components) and α0 is the expansibility of pure water. The expansibilities fit these equations to ±1 p.p.m. and at 35‰ S agree within ±1 p.p.m. with the expansibilities obtained for natural seawater from Knudsen's tables.Theoretical density and expansibility constants have been determined from the apparent equivalent volumes and expansibilities of the major components of seawater by using the additivity principle. The average deviations of the calculated densities and expansibilities are, respectively, ±20 and ±3 p.p.m. over the entire temperature range.  相似文献   

6.
Laboratory investigations were conducted on the formation of NaF° ion-pairs at the ionic strength of seawater using specific ion electrodes. Sodium and fluoride ion electrodes produced results which are consistent with the ion-pairing model for these ionic interactions. The stoichiometric association constant for NaF°, K1NaF, was determined at 15, 25, and 35°C. It was assumed that K1NaF was a function of temperature, pressure, and ionic strength but not of solution composition. The value for K1NaF at 25°C and I = 0.7 m is 0.045 ± 0.006. K1NaF increased with decreasing temperature. This result was used to recompute values of K1MgF and K1CaF accounting for the presence of NaF° ion-pairs. The value for K1NaF indicates that 1.1% of the fluoride in seawater is ion-paired with sodium at 25°C and 35‰ salinity. This fraction increases to approximately 2% at the lower temperatures found in the deep ocean. The percentage of free fluoride in natural seawater was measured at 15, 25, and 35°C to verify the speciation calculated from equilibrium constants.  相似文献   

7.
Examination of the consequences of the stoichiometric association constant K1a = 41.7 for MgSO4 in seawater as advocated by Johnson and Pytkowicz (1979) leads to a thermodynamic association constant Ka = 212.6, a value 32% greater than KA = 160 derived from conductance data. Use of Ka = 160 leads to a K1a in essential agreement with the value of 10.2 reported by Kester and Pytkowicz (1969).  相似文献   

8.
Equilibrium constants for copper(II)-carbonate and -bicarbonate species have been determined at 25°C from consideration of malachite, Cu2(OH)2CO3(s), solubility in UV-photo-oxidized perchlorate solutions of 0.72 m ionic strength. The ratios of total dissolved copper, T(Cu), to free copper(II) ion, [Cu 2+], in 30 malachite saturated experimental solutions of 1–10 × 10?3eq kg?1 H2O initial total alkalinity (TAi in the pH range 5.0–9.3 were fitted to a copper(II)-ion speciation model. The experimental data indicate the existence of CuCO3+, CuHCO3+ and Cu(OH)CO3? in addition to the hydrolys and Cu(OH)CO3? in addition to the hydrolysis products in the range of conditions defined by this study. The stoichiometric equilibrium constants, applicable to seawater at 0.72 m ionic strength, 25°C and 1 atm are
βCuCO3=[CuCO03][Cu2+][CO2?3]=(1.59±0.03)×106
βCuHCO3=[CuHCO+3][Cu2+][HCO?3]=(2.3±0.3)×102
1βCu(OH)CO3=[Cu(OH)CO?3H[Cu2+][CO2?3]=(7.6±0.3)×10?4
A speciation model employing the equilibrium constants determined in this study and copper(II) hydrolysis constants from previous work suggests that the inorganic speciation in seawater (pH = 8.2, TA = 2.3 meq kg ?1, 25°C) is dominated by the CuCO30 complex (82%) and that only 2.9% of the total inorganic copper exists as the free copper(II) ion. Hydrolysis products, CuOH+ and Cu(OH)20, account for 6.5% while CuHCO3+ and Cu(OH)CO3? species comprise 1.0 and 6.3% of the total inorganic copper, respectively.  相似文献   

9.
The various assumptions implicit in the calculation of acid dissociation constants (based on ionic medium standard states) from potentiometric titrations using a cell with liquid junction (i.e. a pH measuring cell) have been examined. It was concluded that results can be obtained having an accuracy commensurate with the experimental precision. It has been shown that although the precise composition of the medium is a function of the hydrogen ion concentration (because of the protolytic nature of some of the ions in the media, e.g., sulphate and fluoride), the effect of such variations in the medium composition can be compensated for when defining the activity of hydrogen ion on an ionic medium standard state by defining the concentration of hydrogen ion as:
[H]SWS=h(1 + βHSO4ST + βHFET)
where βHSO4 and βHF are the relevant association constants and ST and FT are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (KW) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units):
pKw= 3441.0T+2.256-0.709112 (rms deviation 0.01)
where I is the formal ionic strength of the artificial seawater medium and T is the absolute temperature. The values obtained are in reasonable agreement with those found by previous workers.  相似文献   

10.
Vertical measurements of NH4+, NO3? and N2O concentrations, NO3? and NH4+ uptake, and NH4+ oxidation rates were measured at 5 sites in western Cook Strait, New Zealand, between 31 March and 3 April 1983. Nitrate increased with depth at all stations reaching a maximum of 10.5 μg-atom NO3?N l?1 at the most strongly stratified station whereas NH4+ was relatively constant with depth at all stations (~0.1 μg-atom NH4+N l?1). The highest rates of NH4+ oxidation generally occurred in the near surface waters and decreased with depth. N2O levels were near saturation with respect to the air above the sea surface and showed no obvious changes during 24 h incubation. NH4+ oxidation by nitrifying bacteria may account for about 30% of the total NH4+ utilization (i.e. bacterial+agal) and, assuming oxidation through to NO3?, may supply about 40% of the algal requirements of NO3? in the study area. These results suggest that bacterial nitrification is of potential importance to the nitrogen dynamics of the western Cook Strait, particularly with respect to the nitrogen demands of the phytoplankton.  相似文献   

11.
The apparent solubility product of aragonite in 32‰ seawater at 25.0°C is reported as Ksp = (0.869±0.049) × 10?6(mol2kgseawater?2) thus confirming the value of R.A. Berner, 1976 (Am. J. Sci., 276: 713–730). The apparent solubility product ratio for aragonite and calcite is reported as K′aragoniteK′calcite = 2.05 The deviation of this value from the thermodynamic ratio is atttributed to the formation of a stable low Mg-calcite coating on pure calcite in seawater measurements of solubility.  相似文献   

12.
Losses of 15N labelled nitrogen in a Spartina alterniflora salt marsh was measured over three growing seasons. Labelled NH4+N equivalent to 100 μg 15N g?1 of dry soil was added in four instalments over an eight week period. Recovery of the added nitrogen ranged from 93% 5 months after addition of the NH4+N to 52% at the end of the third growing season which represented a nitrogen loss equivalent to 3·4 gNm?2. The availability of the labelled NH4+N incorporated into the organic fraction was estimated by calculation of the rate of mineralization. The time required for mineralization of 1% of the tagged organic N increases progressively with succeeding cuttings of the S. alterniflora and ranged from 152 to 299 days. Only 2% of the nitrogen applied as 15N labelled plant material to the marsh surface in the fall could be accounted for in S. alterniflora the following season.  相似文献   

13.
14.
Spectrophotometric measurements are reported for the first apparent dissociation constant of hydrogen sulfide in seawater over the temperature range 7.5–25°C and 2–35.8‰ salinity. These data are described by the expression pK1′ = 2.527 ? 0.169 Cl13 + 1359.96/T. The second apparent dissociation constant in potassium chloride solution was estimated potentiometrically using a sulfide specific ion electrode. A value of ~13.6 was found for pK2′ at a KCl concentration of 0.67 M. It is suggested that explicit reference to the sulfide ion, S2?, in describing equilibria in marine waters be dropped in favor of a formulation involving the bisulfide ion, HS?.  相似文献   

15.
The three dissociation constants of phosphoric acid have been determined in seawater media over the temperature and ionic strength ranges 5–30°C and 0.3-0.9 m. The results obtained fitted the equations (concentrations in mol per kg of solution):
pK1P=-75T+2.16-0.35I12 (rmsdeviation 0.034)
pK2P=737.6T++4.176-0.851I12 (rmsdeviation 0.015)
pK3P=2404T+1.31-0.87I12 (rmsdeviation 0.17)
The results are only in moderate agreement with those of Kester and Pytkowicz (1967). The reason for this lies partly in differences between the pH scales adopted and partly in the poor precision inherent in their method.  相似文献   

16.
The present investigation examines a vertical cylinder and a horizontal cylinder in progressive waves. The physical differences between the flows are explored and experimental results are compared to previous planar harmonic flow measurements. It is found that modifications to the usual Morison approach are required in some cases to adequately account for the orbital motions of the fluid and to account for the orientation of the orbits with respect to the cylinder axis. The axial variations of the wave force on vertical cylinders are considered in order to evaluate the common practice of assuming constant values of Cmand CD over the entire span. Lastly, the methods of computing force transfer coefficients from a force record are examined and several sources of error are identified and briefly discussed.  相似文献   

17.
The concentration of Ni in C. edule ranges from 17·8 μg/g to 53·82 μg/g with the highest concentration in the gills and mantle and the lowest in the foot and adductor muscles. The concentration does not change with either size or season.There is no significant increase in mortality even in the highest Ni concentration (100 μg/litre), nor is body condition correlated with experimental Ni concentrations. The rate of uptake of Ni (y) is described by the equation:
y=?16·903+11·674x1+0·437x2
where x1 = Ni concentration (μg/litre) and x2 = time (h).The respiration rates did not significantly change up to the highest Ni concentration used (1000 μg/litre).It is postulated that the main pathway for Ni uptake is through the gills, possibly through mucus sheet or transmembrane absorption, with a secondary uptake route via the viscera.C. edule may therefore be a suitable indicator species for Ni.  相似文献   

18.
The addition of various concentrations (1, 10 and 20 mM) of Group VI anions to sediment slurry resulted in inhibition of the rate of sulphate reduction at the two higher concentrations, the degree of inhibition being in the order of molyb-date (MoO4=)>selenate(SeO4=)>tungstate(WO4=). The addition of 20 mM concentrations of these inhibitors almost entirely eliminated sulphate reduction. Doubling the sulphate concentration while using the highest concentration of inhibitors (20 mM) led to the re-establishment of some sulphate reduction in the SeO4= and WO4= treated slurries whereas no such reversal was noticed with MoO4=. These observations suggested that SeO4= and WO4= are competitive inhibitors of sulphate reduction, while MoO4= is a non-competitive inhibitor.  相似文献   

19.
Iron solubility equilibria were investigated in seawater at 36.22‰ salinity and 25°C using several filtration and dialysis techniques. In simple filtration experiments with 0.05 μm filters and Millipore ultra-filters, ferric chlorides fluorides, sulfates, and FeOH2+ species were found to be insignificant relative to Fe(OH)2+ at p[H+] = ?log [H+] greater than 6.0. Hydrous ferric oxide freshly precipitated from seawater yielded a solubility product of 1Kso = [Fe3+][H+]?3 = 4.7 · 105. Solubility studies based on the rates of dialysis of various seawater solutions and on the filtration of acidified seawater solutions indicated the existence of the Fe(OH)30 species. The formation constant for this species can be calculated as 1β3 = [Fe(OH)30] [H+]3/[Fe3+] = 2.4 · 10?14. The Fe(OH)4? species is present at concentrations which are negligible compared to Fe(OH)2+ and Fe(OH)30 in the normal pH range of seawater. However, there is at least one other significant ferric complex in seawater above p[H+] = 8.0 (possibly with bicarbonate, carbonate, or borate ions) in addition to the Fe(OH)2+ and Fe(OH)30 species.  相似文献   

20.
M.D Kumar 《Marine Chemistry》1983,14(2):121-131
A model is presented which signifies the role of oxygen (as oxides and hydroxides) in controlling the composition of seawater. Using the regression equations
log KSW=-0.77+0.03ΔO2-M and [M]SW=KSW[M]crust
logt=4.73+0.04ΔO2-M
respective concentration and residence times for the unknown elements can be estimated. Geometric and statistical indices of Legget and Williams (1981) are used to evaluate the accuracy of the model. This reveals from the known values of ΔO2?M that the present model estimates log ty values within a factor of 1.77. The predicted oceanic residence times for Am, Ir, Ra and Rh are 3.6 × 102, 3.7 × 102, 2.2 × 105 and 6.4 × 102 years, respectively.  相似文献   

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