Solubility of hydrous ferric oxide and iron speciation in seawater

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.     

离子色谱法测定海水中氯离子和硫酸根离子

氯离子和硫酸根离子是海水中重要的无机阴离子,在研究海洋生态变化、海洋循环作用过程与海洋全球气候变化等领域具有重要的指示意义。其测定方法较多,但缺少相应的测试方法。本文对测定海水中Cl^–,SO₄^2–的离子色谱方法进行了优化,选用IonPacAS14碳酸盐选择性离子色谱柱,以3.5mmol/L Na₂CO₃+1 mmol/L NaHCO₃为流动相,可消除海水样品中碳酸盐及其他阴离子的干扰。该方法对Cl^–检出限为0.29mg/L,线性相关系数r²=0.999 2,对SO₄^2–检出限为0.42mg/L,线性相关系数r²=0.997 9。样品的加标回收率在95%～102%,Cl^–和SO₄^2–的相对标准偏差分别为1.92%和4.18%。该方法简便、迅速、灵敏、准确度高,可满足批量海水样品中Cl<...     

Formation and stability of mixed Mg/Ca/phytate species in synthetic seawater media: Consequences on ligand speciation

The results of a potentiometric investigation (by ISE-H⁺, glass electrode) on the speciation of phytate ion (Phy¹²⁻) in an ionic medium simulating the major components (Na⁺, K⁺, Ca²⁺, Mg²⁺, Cl⁻ and SO₄²⁻) of natural seawater, at different salinities and t = 25 °C, are reported. The work was particularly aimed at determining the possible formation of mixed Ca²⁺–Mg²⁺–phytate ion pairs, and to establish how including the formation of these mixed species would affect the speciation modeling in seawater media. After testing various speciation models, that considering the formation of the MgCaH₃Phy⁵⁻, MgCaH₄Phy⁴⁻, Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ species was accepted, and corresponding stability constants were determined at two salinities (S = 5, 10). A discussion is reported both on the choice of the experimental conditions and on the possibility to extend these results to those typical of real seawater. A detailed procedure is also described to demonstrate that the stability of these species is higher than that statistically predicted. As reported in literature, a parameter, namely log X, has been determined in order to quantify this extra stability for the formation of each mixed species at various salinities. For example, at S = 10, log X₁₁₃ = 2.67 and log X₁₁₄ = 1.37 for MgCaH₃Phy⁵⁻ and MgCaH₄Phy⁴⁻ (statistical value is log X_stat = 0.60), and log X₂₁₃ = 6.11 and log X₂₁₄ = 2.15 for Mg₂CaH₃Phy³⁻ and Mg₂CaH₄Phy²⁻ (log X_stat = 1.43), respectively. Results obtained also showed that the formation of these species may occur even in conditions of low salinity (i.e. low concentration of alkaline earth cations) and low pH (i.e., more protonated ligand).     

A study on the chemical forms of radionuclides in seawater—II chloride and sulfate complexes of60Co

The apparent stability constants for chloride and sulfate ions with Co (II) at ionic strength of 0.67 were determined by the cation exchange method. The value of the stability constant ₁ for chloride ion with Co (II) ion was 0.79±0.055. The stability constants ₁, ₂ and ₃ for sulfate ion with Co (II) ion were 12.0±0.27, 91.5±11.4 and l,110±250, respectively. The chemical species of Co (II) in seawater was estimated at the pH of 8.0 to be present as Co²⁺ (63%), CoCl⁺ (27%) and CoSO₄ ⁰ (8.6%) using the known value of dissociation constant of Co (II), and under the assumption that only major inorganic anions are responsible for the chemical equilibrium of Co (II).     

The stability and reproducibility of Tris buffers in synthetic seawater

The equimolal Tris buffer (0.04 mol/kg-H₂O Tris + 0.04 mol/kg-H₂O Tris-HCl) prepared in synthetic seawater of salinity 35 has been shown to be stable when sealed in a borosilicate glass bottle with a greased ground-glass stopper (drift rate ≤ 0.0005 in pH per year). The error in pH of such buffers resulting from uncertainties in the preparation of such buffers is typically less than 0.002 in pH (relative to the results of DelValls and Dickson, 1998 [DelValls, T.A., Dickson, A.G., 1998. The pH of buffers based on 2-amino-2-hydroxymethyl-1,3-propanediol (‘tris’) in synthetic sea water. Deep-Sea Research I, 45, 1541–1554]).     

Hydrogen ion exchange on amorphous silica in seawater

The amount of hydrogen ion exchange on the surface of amorphous silica in seawater was measured as a function of pH at 2 and 25°C. Hydrogen ion exchange with the cations present in seawater is pH dependent and at 25°C the fraction of the surface in the cation form increases from 9% at pH 7 to 22% at pH 8. The exchange is temperature dependent and at 2°C and pH 8, 14% of the exchange sites are occupied by cations, as opposed to 22% of the exchange sites at 25°C. These results were used to calculate the buffer capacity of a model sediment consisting of pore water and amorphous silica. For a sediment of 70% porosity, pH 7.7, and 25°C, the buffer capacity of sediment plus pore water is 67 times the buffer capacity of pure seawater.     

Dissociation constants of protonated cysteine species in seawater media

The dissociation constants (pK₁, pK₂ and pK₃) for cysteine have been measured in seawater as a function of temperature (5 to 45 °C) and salinity (S = 5 to 35). The seawater values were lower than the values in NaCl at the same ionic strength. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been compared to those calculated from the Pitzer ionic interaction model. The lower values of pK₃ in the Na–Mg–Cl solutions have been attributed to the formation of Mg²⁺ complexes with Cys²⁻ anions

Mg²⁺ + Cys²⁻ = MgCys

The stability constants have been fitted to

after corrections are made for the interaction of Mg²⁺ with H⁺.The pK₁ seawater measurements indicate that H₃Cys⁺ interacts with SO₄²⁻. The Pitzer parameters β⁰(H₃CysSO₄), β¹(H₃CysSO₄) and C(H₃CysSO₄) have been determined for this interaction. The formation of CaCys as well as MgCys are needed to account for the values of pK₂ and pK₃ in seawater.The consideration of the formation of MgCys and CaCys in seawater yields model calculated values of pK₁, pK₂ and pK₃ that agree with the measured values to within the experimental error of the measurements. This study shows that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

Dissociation constants of protonated methionine species in seawater media

The dissociation constants (pK₁ and pK₂) for methionine have been measured in artificial seawater as a function of salinity (S = 5 to 35) and temperature (5 to 45 °C). The seawater pK₂ values were lower than the values in NaCl at the same ionic strength while the pK₁ values in seawater were lower only at S = 35. In an attempt to understand these differences, we have made measurements of the constants in Na–Mg–Cl solutions at 25 °C. The measured values have been used to determine the formation of Mg²⁺ complexes and Pitzer interaction parameters for Mg²⁺ with methionine. The seawater model with the interaction parameters accounts for the differences between the value of pK₁ and pK₂ between NaCl and seawater. This study demonstrates that it is important to consider all of the ionic interactions in natural waters when examining the dissociation of organic acids.     

自动电位滴定仪高效高精度测定海水碱度值

为研究海洋碳循环和海洋碳酸盐系统,需要测定样品的碳酸盐碱度。利用电位滴定仪(万通~(?)798MPT Titrino)配合软件tiamol.1检测了海水总碱度。根据碳酸盐解离常数计算出了海水碳酸盐碱度,相时标准偏差低于0.1%(±2μmol/kg),单个样品用量约25 mL,检测时间约9 min。实验结果表明,用自动电位滴定仪测定海水总碱度速度快,精度高,方法可行。     

Clay migration and entrapment in synthetic porous media

Water-sensitivity in sandstones is commonly ascribed to mobilization, transport and recapture of clays in downstream pore throats. This is based mainly on knowledge of the clay mineral content and its electrochemistry. This paper describes a method for directly observing water-sensitivity mechanisms under the microscope using pore networks etched in glass, with clays introduced into the networks. This allows direct identification of colloidal and transport factors, which is not possible in sandstone cores. The migration behaviour has been investigated with variations in flow rate, acceleration forces and salinity. Migration was observed to occur in two distinct modes: (1) as flocs, especially in concentrated brines and at high flow rates, (2) as deflocculated individual particles, especially in distilled water. Recapture of clays occurs by the formation of ‘particle briges’. The upstream pressure indicates that particle recapture is related to decreasing permeability.     

Interconversion of iron(III) hydroxy complexes in seawater

Interconversion rates of the mononuclear ferric iron species Fe(OH)₃⁰ and Fe(OH)₂⁺ are derived and their implications for the behavior of these species in seawater are examined. The previously reported formation constant for Fe(OH)₃⁰ and its claimed extreme adsorptive reactivity in seawater are shown to be mutually inconsistent. Although Fe(OH)₃⁰ is probably a stoichiometrically minor dissolved iron species, its rapid formation from Fe(OH)₂⁺ could substantially enhance the rates of heterogeneous reaction rates of the [Fe(OH)₂⁺ + Fe(OH)₃⁰] pool if the latter species is very reactive.     

A field study of physico-chemical states of artificial radionuclides in seawater

The physico-chemical states of artificial radionuclides,⁹⁰Sr,¹³⁷Cs and¹⁴⁴Ce in seawater were investigated by radiochemical analysis of filtered and unfiltered seawater. The difference of radionuclide concentrations between unfiltered and filtered seawaters was defined as the particulate form radioisotope and its particle ratio was discussed.Practically no particulate⁹⁰Sr, greater than 0.22 in size, was observed in both coastal and open seawaters, but some of¹³⁷Cs seemed to be insoluble in some circumstances, especially in coastal waters. A considerable amount of¹⁴⁴Ce was found to be particulate.An estimation of the radionuclides in particulate form was made for Kashima-nada seawaters collected in 1970 to 1972, and it was shown that the possible occurrence of particulate radionuclides, greater than 0.22 in size, were 1% or less for⁹⁰Sr and 6% for¹³⁷Cs. In the coastal water, 80 % of¹⁴⁴Ce were seemed to be in particulate form, but in the open seawater only a few%. The influences of suspended materials to¹³⁷Cs and¹⁴⁴Ce concentration levels in seawater were not negligible and further investigations are desirable.     

Application of potentiometric method using a cell without liquid junction to underway pH measurements in surface seawater

This study evaluated a method to carry out underway pH measurements of surface seawater by means of a cell without liquid junction using glass electrodes for hydrogen and sodium ions as follows:

Glass-electrode-Na+

Test solution (reference solution)

H+-glass-electrode

Full-size table

Table options

     

15.

Detection of free polyamine in coastal seawater using ion exchange chromatography     

Nishibori  Naoyoshi; Nishii  Akinori; Takayama  Haruyoshi 《ICES Journal of Marine Science》2001,58(6):1201-1207

     

16.

A synthetic aperture sonar system capable of operating at high speed and in turbulent media     

Gough  P. 《Oceanic Engineering, IEEE Journal of》1986,11(2):333-339

Despite their potential ability to produce highly resolved images of the seabed, synthetic aperture sonars are not widely used. The primary reason for this restricted use is that most synthetic aperture systems are based on the radiation and detection of short-duration modulated pulses. Due to the low speed of sound in water, the pulse repetition frequency is low and so it has been difficult to maintain the required pulse-to-pulse phase coherence. This paper describes a new approach to synthetic aperture sonars based on continuous transmission with some form of frequency modulation. That is, a sonar that transmits and receives continuously but uses some form of frequency coding (in this case a linear frequency sweep) to determine range. Using a continuous transmission frequency modulated sonar it is possible to make a synthetic aperture sonar that can produce coherent apertures many wavelengths long. In addition to the combination of synthetic apertures and continuous transmission frequency modulation, further modifications are suggested to reduce the effect of lateral towfish movement and the effects of medium turbulence resulting in random path-length variations.     

17.

Metal-organic complexes in seawater pumped up from under the ground     

Noburu Takematsu  Yoshio Sato  Shiro Okabe 《Journal of Oceanography》1983,39(6):305-309

Metal-organic complexes of transition elements removed by Amberlite XAD-2 resin from seawater pumped up from under the ground were determined. The proportions of iron, copper and zinc retained on the resin to dissolved forms of these metals were about 70, 40 and 5%, respectively, while manganese, cobalt and nickel were not retained on the resin. These results suggest that although iron may be retained in colloidal form, a significant fraction of copper is present in some organic form(s).     

18.

厦门湾富营养化程度趋势变化研究   总被引：2，自引：2，他引：2  

林辉  ZHANG Yuan-biao 《台湾海峡》2008,27(3)

本文根据2003～2006年厦门湾水质调查资料,研究了水体中化学耗氧量(COD)、溶解态无机氮(DIN)和磷酸盐(PO43--P)的含量分布及该海域富营养化程度的变化趋势.结果表明,近4a来,厦门湾COD平均含量呈现下降趋势;而水体的DIN和PO43--P平均含量呈增加趋势.厦门湾水体中平均N/P大于16,主要表现为磷限制特征,而马銮湾海区则表现为"丰磷"状态.厦门湾水体富营养化指数由1.1增加至5.4,增加趋势明显.     

19.

A comment on ‘MgSO4 ion association in seawater’ by Fisher,Gieskes and Hsu     

Kenneth S Johnson 《Marine Chemistry》1982,11(3):285-286

Recently, the stoichiometric association constant for MgSO₄^o in seawater was presented as being inconsistent with thermodynamic data. The results obtained are refuted here as being inaccurate due to assumptions made concerning the activity coefficient of the MgSO₄^o ion pair.     

20.

A note on the polarographic behavior of the Cu(II) ion selective electrode in seawater     

Alberto Zirino  Peter F. Seligman 《Marine Chemistry》1981,10(3):249-255

The non-Nernstian behavior of a solid-state cupric ion-selective electrode in seawater is attributed to a reduction of Cu²⁺ at the surface in accordance with a suggestion made in the literature. This ‘polarographic’ behaviour was demonstrated by showing that the electrode potential is affected by molecular oxygen in solution.     

A synthetic aperture sonar system capable of operating at high speed and in turbulent media

Despite their potential ability to produce highly resolved images of the seabed, synthetic aperture sonars are not widely used. The primary reason for this restricted use is that most synthetic aperture systems are based on the radiation and detection of short-duration modulated pulses. Due to the low speed of sound in water, the pulse repetition frequency is low and so it has been difficult to maintain the required pulse-to-pulse phase coherence. This paper describes a new approach to synthetic aperture sonars based on continuous transmission with some form of frequency modulation. That is, a sonar that transmits and receives continuously but uses some form of frequency coding (in this case a linear frequency sweep) to determine range. Using a continuous transmission frequency modulated sonar it is possible to make a synthetic aperture sonar that can produce coherent apertures many wavelengths long. In addition to the combination of synthetic apertures and continuous transmission frequency modulation, further modifications are suggested to reduce the effect of lateral towfish movement and the effects of medium turbulence resulting in random path-length variations.     

Metal-organic complexes in seawater pumped up from under the ground

Metal-organic complexes of transition elements removed by Amberlite XAD-2 resin from seawater pumped up from under the ground were determined. The proportions of iron, copper and zinc retained on the resin to dissolved forms of these metals were about 70, 40 and 5%, respectively, while manganese, cobalt and nickel were not retained on the resin. These results suggest that although iron may be retained in colloidal form, a significant fraction of copper is present in some organic form(s).     

厦门湾富营养化程度趋势变化研究

本文根据2003～2006年厦门湾水质调查资料,研究了水体中化学耗氧量(COD)、溶解态无机氮(DIN)和磷酸盐(PO43--P)的含量分布及该海域富营养化程度的变化趋势.结果表明,近4a来,厦门湾COD平均含量呈现下降趋势;而水体的DIN和PO43--P平均含量呈增加趋势.厦门湾水体中平均N/P大于16,主要表现为磷限制特征,而马銮湾海区则表现为"丰磷"状态.厦门湾水体富营养化指数由1.1增加至5.4,增加趋势明显.     

A comment on ‘MgSO4 ion association in seawater’ by Fisher,Gieskes and Hsu

Recently, the stoichiometric association constant for MgSO₄^o in seawater was presented as being inconsistent with thermodynamic data. The results obtained are refuted here as being inaccurate due to assumptions made concerning the activity coefficient of the MgSO₄^o ion pair.     

A note on the polarographic behavior of the Cu(II) ion selective electrode in seawater

The non-Nernstian behavior of a solid-state cupric ion-selective electrode in seawater is attributed to a reduction of Cu²⁺ at the surface in accordance with a suggestion made in the literature. This ‘polarographic’ behaviour was demonstrated by showing that the electrode potential is affected by molecular oxygen in solution.