Prediction of the partial molal volumes of electrolytes in seawater     

J.V. Leyendekkers 《Marine Chemistry》1974,2(2):89-110

A general equation is derived for predicting the partial molal volume (pmv) of an electrolyte in seawater, using binary solution data, and seawater density data. The composition of seawater need not be “average” - prediction can be made for any composition. Simpler equations are derived for “average” seawater. The ranges cover $\text{S = 0–50‰}$, t = 0–30°C and p = 1–1,000 bar, subject to the availability of binary solution data. Estimates of the pmv's of a number of electrolytes are made and compared with experimental values and the summed ionic values.  相似文献   

The refractive index of seawater — comparison of experimental values and estimates from binary solution data     

J.V. Leyendekkers  R.J. Hunter 《Marine Chemistry》1978,6(1):71-76

The Tait-Gibson parameter, $\text{B}{}^1$, and the refractive index of seawater are estimated from binary solution data. The predicted and experimental values agree closely. The maximum deviations, at $\text{S = 40‰}$, are 1.7 bars for $\text{B}{}^1$ and 0.0001 for the refractive index. The results show that binary solution data, analysed on the basis of the Tammann-Tait-Gibson model for aqueous solutions, can be used to predict the properties of seawater of composition different to that of standard seawater.  相似文献   

‘Reactive’ and ‘unreactive’ iodine in seawater — A possible indication of an organically bound iodine fraction     

Victor W. Truesdale 《Marine Chemistry》1975,3(2):111-119

An iodine component in seawater, which is ‘unreactive’ to the total inorganic method described by Truesdale and Spencer (1974), has been discovered. The component is measured as the increase in ‘reactive’ iodine that accompanies irradiation of seawater with high-intensity UV light. The highest concentration recorded for an inshore water was $\text{5.2 ± 0.5}\text{μg/l}$. As some known organic-iodine compounds behave in a similar manner to UV irradiation, it is suggested that the ‘unreactive’ iodine is organically bound iodine.  相似文献   

Characterisation of domestic and industrial sewage in Southern California coastal sediments using nitrogen,carbon, sulphur and uranium tracers     

R.E. Sweeney  E.K. Kalil  I.R. Kaplan 《Marine environmental research》1980,3(3):225-243

A degradation-mixing model has been developed to aid in the interpretation of geochemical processes occurring in sewage-contaminated marine sediment near San Pedro, California. The nitrogen isotope ratio (${}^{15}{}^{14}\text{N}$) is shown to be an effective tracer of sewage discharge-on the San Pedro Shelf. Isotopic fractionation of ${}^{15}\text{N}{}^{14}\text{N}$ during release of amino compounds or ammonia (as a consequence of bacterial degradation of organic detritus) appears to be negligible. The nitrogen isotope ratio, therefore, may be considered a conservative component for tracing the source of organic matter deposited in marine sediment.Uranium enrichment from seawater is shown not to occur in the highly reducing sewage-contaminated sediments. The content of uranium in the effluent particulates (18 ppm) is large compared with the content in the uncontaminated sediment (3 to 5 ppm). This allows the content of uranium to also be used as a tool for tracing the deposition of sewage particles in marine sediment. Uranium and nitrogen are shown to be incorporated in the organic fraction of sewage effluent and are released during bacterial degradation of the organic matter. Cadmium and sulphur are shown not to be mobilised during sewage deposition and degradation. The stable isotope ratio of sulphur (${}^{34}\text{S}{}^{32}\text{S}$) is used to demonstrate that sulphur enrichment occurs in the sediment by in situ reduction of seawater sulphate. The data summarised by Morel et al. (1975) are presented and discussed in accordance with the above model.  相似文献   

Determination of nitrate in seawater: Nitrate to nitrite reduction with copper-cadmium alloy     

D.J. Hydes  N.C. Hill 《Estuarine, Coastal and Shelf Science》1985,21(1):127-130

Determination of nitrate in seawater first requires its reduction to nitrite. Construction of a reductor column for use during continuous flow analysis at sea is described. Novel use is made of an alloy of cadmium and copper ($\text{50}\text{50}\text{w}\text{w}$) crushed to between 500 and 350 μm. Its performance is similar to that of the cadmium wire type of reductor but offers advantages of easier preparation and control of reductor volume.  相似文献   

Double-diffusive convection with a nonlinear equation of state: Part II. Laboratory experiments and their interpretation     

Trevor J. McDougall 《Progress in Oceanography》1981,10(2):91-121

The term cabbeling describes the convection that can occur when a mixture of two oceanic water masses is more dense than both of the parent water masses. When the two water masses are situated one above the other, the temperature and salinity distributions are in the correct senses for double-diffusive convection to occur and it is found that the prime effects of the nonlinearity of the equation of state are firstly to drive a greater level of double-diffusive convective activity in the lower layer than in the upper layer, and secondly, to make the lower edge of the interfacial region less gravitationally stable. Both of these effects cause the interface to migrate upwards as the lower layer grows at the expense of the upper layer. We introduce a nondimensional parameter $\text{δ}$ (called the cabbeling parameter) which represents the importance of the nonlinearity of the equation of state:—$\text{δ}$ is zero when the equation of state is linear and when cabbeling is normally thought to be possible, $\text{δ}$ is greater than unity. Experiments set up in both the finger and diffuse sense show how the nondimensional measure of the upward interface migration (called the “entrainment” parameter $\text{E}$) varies with the density anomaly ration R_? for various values of $\text{δ}$ between zero and 2.0 and that no abrupt change in this behaviour occurs at $\text{δ}\text{= 1.0}$. It is impossible to explain these observation by neglecting double-diffusive convection and considering only the convection driven by the conventional cabbeling instability. The successful interpretation of the laboratory results relies on considering the effects of a non-linear equation of state on the double-diffusive convection process.  相似文献   

Geochemistry of manganese deposits in relation to environment on the sea floor around southern Africa     

C.P. Summerhayes  J.P. Willis 《Marine Geology》1975,18(4):159-173

Manganese deposits from the Madagascar Basin, the Crozet Basin and the basins west of the Madagascar Ridge around southern Africa differ chemically from one another. This appears to be largely because of differences in the degree of oxygenation of the environment; most highly oxidizing is the Madagascar Basin, where the $\text{Mn}\text{Fe}$ ratio is very low and where the manganese deposits probably consist largely of “birnessite”.Continental-margin samples differ from basin samples in having higher $\text{Mn}\text{Fe}$ ratios, probably because of diagenetic remobilization processes within the sediment column. The ratios of Mn and Fe to certain metals ($\text{Mn}\text{Ni}$, $\text{Mn}\text{Zn}$, $\text{Fe}\text{Co}$ and $\text{Fe}\text{As}$) are the opposites of those found in other continental-margin environments, suggesting either a difference in the diagenetic process, or an additional metal source, off southern Africa. Both seawater and bottom sediments of the southern African margin are metal-enriched, and could act as sources of metals for growing manganese nodules and encrustations.  相似文献   

Composition of Pacific Ocean ferromanganese nodules     

David Z. Piper  Michael E. Williamson 《Marine Geology》1977,23(4):285-303

Bulk composition of ferromanganese nodules from the pelagic environment of the Pacific Ocean is apparently related to nodule-growth rate, sediment-accumulation rate, and biologic productivity in the overlying seawater. Nodules with a high $\text{Mn}\text{Fe}$ ratio and high Ni and Cu concentrations tend to occur in areas where primary productivity in the surface layer of the ocean is high and the sediment-accumulation rate low. Nodules with a low $\text{Mn}\text{Fe}$ ratio and low Ni and Cu concentrations occur in areas either where sediment-accumulation rate is high or biologic productivity is low. They may have a $\text{Mn}\text{Fe}$ ratio as low as one and accrete at rates as low as $\text{1}\text{mm}\text{10}{}^6\text{yrs}$. Nodules with a larger $\text{Mn}\text{Fe}$ ratio apparently have growth rates that are greater by as much as a factor of 10.  相似文献   

The density and expansibility of artificial seawater solutions from 0 to 40°C and 0 to 21‰ chlorinity     

Frank J. Millero  Fred K. Lepple 《Marine Chemistry》1973,1(2):89-104

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, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and an equation based on the Debye-Hückel limiting law, $\text{d = d}{}^0\text{+}\text{A}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{V}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_V′, B_V′, A_V, B_V and C_V 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 Cl_V is the volume chlorinity — $\text{Cl}{}_{\mathrm{V}}\text{= Cl (‰) × density}$. 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 $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{′ Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{α = α}{}^0\text{+}\text{A}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}\text{+ B}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{+ C}{}_{\mathrm{E}}\text{Cl}{}_{\mathrm{V}}{}^2$ where A_E′, B_E′, A_E, B_E and C_E 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   

Sodium fluoride ion-pairs in seawater     

Gerard R. Miller  Dana R. Kester 《Marine Chemistry》1976,4(1):67-82

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°, $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$, was determined at 15, 25, and 35°C. It was assumed that $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ was a function of temperature, pressure, and ionic strength but not of solution composition. The value for $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ at 25°C and I = 0.7 m is 0.045 ± 0.006. $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ increased with decreasing temperature. This result was used to recompute values of $\text{K}{}^1{}_{\mathrm{<mtext>MgF</mtext>}}$ and $\text{K}{}^1{}_{\mathrm{<mtext>CaF</mtext>}}$ accounting for the presence of NaF° ion-pairs. The value for $\text{K}{}^1{}_{\mathrm{<mtext>NaF</mtext>}}$ 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   

Tracing flocculent industrial and domestic sewage transport on San Pedro Shelf,Southern California,by nitrogen and sulphur isotope ratios     

Robert E. Sweeney  I.R. Kaplan 《Marine environmental research》1980,3(3):215-224

Domestic and industrial sewage is discharged at a depth of 60 m near Whites Point on the San Pedro Shelf, Southern California borderland. A density-stratified thermocline, above the outfall at a depth of 20 to 30 m, is thought to prevent most effluent particles from reaching shallower depths and recreational facilities. In this investigation, measurement of the natural abundance of nitrogen isotopes (${}^{15}\text{N}{}^{14}\text{N}$) is used to determine the level of sewage contribution to flocculent suspended material persisting at water depths of 7, 13 and 20 m. Organic nitrogen at 20 m depth was shown to be predominantly of sewage-origin and at 7 m, predominantly of marine origin. Organic nitrogen at 13 m depth and within 3 km of the outfall pipes is predominantly sewage in origin.Stable isotope composition of sulphur (${}^{32}\text{S}{}^{34}\text{S}$) in the flocculent material indicates that the effluent particles contain metabolic sulphur, incorporated from dissolved seawater, as well as bacterially produced mineral sulphide.  相似文献   

The influence of suspended cohesive sediments on boundary-layer structure and erosive activity of turbulent seawater flow     

Giselher Gust  Eckart Walger 《Marine Geology》1976,22(3):189-206

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 $\text{u}{}_{\mathrm{<mtext>1\; </mtext><mtext>crit</mtext>}}$ 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   

The estimation of acid dissociation constants in seawater media from potentionmetric titrations with strong base. I. The ionic product of water — Kw     

A.G Dickson  J.P Riley 《Marine Chemistry》1979,7(2):89-99

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: where β_HSO4 and β_HF are the relevant association constants and S_T and F_T are the total concentrations of sulphate and fluoride, respectively.This approach was used to obtain values for the ionic product of water (K_W) in artificial seawater media at various temperatures and ionic strengths. These were fitted to give the equation (molal concentration units): 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   

Solubility of hydrous ferric oxide and iron speciation in seawater     

Robert H. Byrne  Dana R. Kester 《Marine Chemistry》1976,4(3):255-274

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 ${}^1\text{K}{}_{\mathrm{<mtext>so</mtext>}}\text{=}\text{[Fe}{}^{\mathrm{3+}}\text{][H}{}^{\mathrm{+}}\text{]}{}^{\mathrm{?3}}\text{= 4.7 · 10}{}^5$. 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 ${}^1\text{β}{}_3\text{=}\text{[Fe(OH)}{}_3{}^0\text{] [H}{}^{\mathrm{+}}\text{]}{}^3\text{/[Fe}{}^{\mathrm{3+}}\text{] = 2.4 · 10}{}^{\mathrm{?14}}$. 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   

The solubility of aragonite in seawater at 25.0°C and 32.62‰ salinity     

David C. Plath  Ricardo M. Pytkowicz 《Marine Chemistry》1980,10(1):3-7

The apparent solubility product of aragonite in 32‰ seawater at 25.0°C is reported as K′_sp = (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 $\text{K′}{}_{\mathrm{aragonite}}\text{K′}{}_{\mathrm{calcite}}\text{= 2.05}$ 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   

The effect of pressure on the chemical potentials of seawater components,on ionic species in seawater,and on calcite saturation levels     

J.V. Leyendekkers 《Marine Chemistry》1975,3(1):23-41

The activities of most of the major seawater components at 1,001 bars have been estimated, and values for the ions deduced. Equations giving the effect of pressure on the activities of ionic species in seawater ($\text{S = 35‰}$) have been developed. The species covered are: NaSO₄^?, MgSO₄⁰, CaSO₄⁰, H⁺, the free base (NH₃), the HCO₃^?/CO₃² activity ratio and the ion activity product of calcium carbonate. Comparison of the latter with the “ideal” solubility of calcite (pure solid in equilibrium with a mixed electrolyte solution) indicates a degree of saturation compatible with the trends indicated by in situ measurements.  相似文献   

$\text{Am}\text{-241}\text{Pu}\text{-239 + 240}$ ratios in the marine environment     

M Koide  P.W Williams  E.D Goldberg 《Marine environmental research》1981,5(3):241-246

The $\text{Am}\text{-241}\text{Pu}\text{-239 + 240}$ ratio is at least a factor of two higher in the particulate phases of California coastal waters than the values previously reported for unfiltered waters and sediments. These results are attributed to a greater water solubility for plutonium relative to americium species. The values of the ratio in mussels indicate primarily a particulate uptake of these transuranics. Sorption experiments of these two elements from seawater to glass beads, rayon fibres and filter papers are consistent with an uptake of the particulate phases.  相似文献   

Effect of modification of particle size of emulsions of venezuelan crude oil on feeding,survival and growth of marine zooplankton     

R. Hebert  S.A. Poulet 《Marine environmental research》1980,4(2):121-134

Variations in the natural particle size spectra following the addition of Venezuelan crude oil in seawater ($\text{? 6 μ}\text{l litre}{}^{\mathrm{?1}}$) were related to the mixing speeds of the emulsion and were independent of the oil concentration. The particle spectrum and feeding behaviour of Meganyctiphanes norvegica and Calanus hyperboreus were both modified. Artificially created oil droplets were suitable in size for ready ingestion by zooplankton. The growth and survival of contaminated Acartia hudsonica were rapidly and significantly reduced. Groups under starvation conditions showed similar decreases to those exposed to oil. During a depuration period, treated copepods exhibited growth rates similar to those of untreated specimens. The input and noxious effects of crude oil are discussed with special reference to particle size distribution and chemosensory feeding behaviour.  相似文献   

Wave induced random oscillations of pipelines during laying     

Colin L. Kirk  Essien U. Etok 《Applied Ocean Research》1979,1(1):51-60

A study is presented of wave induced random vibrations of pipelines suspended in the $\text{J-}\text{configuration}$. The analysis is based on the use of Morison's equation for the hydrodynamic forces and a linearized spectral analysis of response in the first five normal modes of oscillation. Three pipelines are studied for an operational sea state of $\text{H}{}_{\mathrm{S}}\text{= 4.57}\text{m}$ and a survival case of $\text{H}{}_{\mathrm{S}}\text{= 12}\text{m}$. Extensive results are given for the expected peak deflections and stresses. Under operational conditions the expected peak stresses were found to be well below the maximum allowable stress for both the pipeline and the concrete coating, but in the survival case the peak stresses were found to be unacceptably high.  相似文献   

MgSO4 ION association in seawater     

F.H Fisher  J.M Gieskes  C.C Hsu 《Marine Chemistry》1982,11(3):279-283

Examination of the consequences of the stoichiometric association constant $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}\text{= 41.7}$ for MgSO₄ in seawater as advocated by Johnson and Pytkowicz (1979) leads to a thermodynamic association constant K_a = 212.6, a value 32% greater than K_A = 160 derived from conductance data. Use of K_a = 160 leads to a $\text{K}{}^1{}_{\mathrm{<mtext>a</mtext>}}$ in essential agreement with the value of 10.2 reported by Kester and Pytkowicz (1969).  相似文献