Ionization of water in seawater

The ion product of water in seawater and the total activity coefficients of hydroxide and hydrogen ions were determined over the temperature range 2° to 35°C, and the salinity range 20‰ to 44‰. At 25°C and 35‰ salinity, the measured values are pK_W^SW = 13.20, f_OH = 0.22, f_H = 0.71 on the molar concentration scale.     

Diffusion coefficients of major ions in seawater

Self-diffusion coefficients of five major ions have been determined by a radioactive tracer method (capillary tube method) in seawater of salinity 34.86 at 25°C. Data are presented for Na⁺, Ca²⁺, Cl⁻, SO₄², and HCO₃⁻, which constitute about 95% by weight of sea salt. The influence of temperature and salinity on these coefficients has been studied for Na⁺ and Cl⁻ which are the major components of sea salt: self-diffusion coefficients of these two ions have been measured in seawater, at different temperatures for a salinity of 34.86 and at different salinities for a temperature of 25°C. Diffusion coefficients of the same ions have been determined at 25°C by using another radioactive tracer method (quasi-steady cell method). In this experiment, seawater ions were allowed to diffuse from natural seawater into dilute seawater. Data have been obtained at 25°C for Na⁺, Ca ²⁺, Cl⁻, SO₄²⁻ and HCO₃⁻, corresponding to different salinity gradients.     

A review of the effect of salts on the solubility of organic compounds in seawater

The presence of electrolytes (salts) in aqueous solution modifies the solubility and related properties of organic compounds in water. Reported data for salting-out constants (Setschenow constants) which relate solubility to the salt concentration of aromatic and alkane hydrocarbons, and their chlorinated derivatives, and some organic acids have been compiled for 25 aqueous salt solutions at 20–25 °C. The salting-out sequences for various electrolytes are discussed and it is shown that the salting-out effect is greater for organic solutes with large molar volumes. A compilation of salting-out constants for NaCl solutions and seawater (natural or synthetic) with a variety of solutes, shows that the Setschenow constants are similar for natural or artificial seawater (at salinity of 30–35%.) and NaCl solutions (at 3.0–3.5% or 0.5 M). A simple correlation is suggested for estimating the Setschenow constants for a variety of organic solutes in seawater which typically yields a reduction in solubility by a factor of 1.36. The hydrophobicity of organic solutes is therefore increased by this factor, as is the air-water partition coefficient, implying an increased partitioning from aqueous solution into air, organic carbon and lipid phases. The effect must be quantified when comparing the behavior of organic contaminants in freshwater and marine conditions.     

The solubility of calcite in seawater at atmospheric pressure and 35%permil; salinity

The apparent (stoichiometric) solubility product of calcite in artificial seawater of salinity 35‰ was measured by a saturometer technique. The value of the apparent solubility product was found to be (4·59 ± 0·05) × 10⁻⁷ moles/(kilogram of seawater)² at 25°C with a temperature coefficient of −0·0108 × 10⁻⁷/°C between 2 and 25°C. These values are significantly smaller than those found by MacIntyre (1965) and other workers. The effect of these results on the saturation of the oceans with respect to calcite is examined.     

A Gibbs–Pitzer function for high-salinity seawater thermodynamics

A high-salinity Gibbs function for seawater is derived from Pitzer equations of the sea salt components, in conjunction with the 2003 Gibbs function of seawater for low salinities. Various properties, computed from both formulations by thermodynamic rules, are compared with each other, and with high-salinity measurements. The new Gibbs–Pitzer function presented in this paper is valid in the range 0–110 g kg⁻¹ in absolute salinity, −7 to +25 °C in temperature, and 0–100 MPa in applied pressure. The formulation is expressed in the International Temperature Scale 1990 (ITS-90), and is consistent with the International Standard for Fluid Water (IAPWS-95), and with the 2005/2006 equations of state of ice Ih.     

Nitrous oxide solubility in water and seawater

The solubility of nitrous oxide in pure water and seawater has been measured microgasometrically over the range 0–40°C. The data have been corrected for nonideality and are fitted to equations in temperature and salinity of the form used previously to fit the solubilities of other gases. The fitted values have a precision of 0.1% and an estimated accuracy of 0.3%. The nonideal behavior of nitrous oxide—air mixtures is discussed, and the solubility of atmospheric nitrous oxide is presented in parametric form. A similar parametric representation for the solubility of atmospheric carbon dioxide is given in the Appendix.     

The diffusion coefficient of dissolved silica revisited

The diffusion coefficient of dissolved silica was determined for two different salinities, 36 and 0, at temperatures ranging from 2 °C to 30 °C and at an average pH value of 8.1. Our results show limited influence of salinity and a variation by a factor of 2 to 3 of the silica diffusion coefficient within the temperature range considered in this study. The values obtained at 25 °C are in agreement with previous work carried out at room temperature for seawater and freshwater. The dependency on temperature and viscosity of the diffusion coefficient agrees well with the Einstein–Stokes equation. The composition of the solvent appears to be an important factor because it modifies the viscosity and allows for the complexation of the dissolved silica with less mobile ions, while its pH controls the dissolved silica speciation. In seawater, the higher viscosity and the presence of dissociated and polymeric species result in a decrease of the diffusion coefficient compared to freshwater systems.     

Solubility of calcite in the ocean

The apparent solubility product K′_sp of calcite in seawater was measured as a function of temperature, salinity, and pressure using potentiometric saturometry techniques. The temperature effect was hardly discernible experimentally. The value of K′_sp at 25°C was 4.59·10⁻⁷ mole²/(kg seawater)² at 35‰S, 5.34·10⁻⁷ at 43‰S, and 3.24·10⁻⁷ at 27‰S. The apparent partial molal volume was found to be −34.4 cm³ at 25°C and −42.3 cm³ at 2°C from a linear fit of log(K′_sp ^P/K′_sp ¹). These results were used in conjunction with field data to calculate the degree of saturation in the oceans and showed undersaturation at shallower depths than previously reported.     

The effect of ionic interaction on the rates of oxidation in natural waters

The effect of ionic interactions on the kinetics of disproportionation of HO₂, and the oxidation of Fe(II) and Cu(I) has been examined. The interactions of O₂ with Mg²⁺ and Ca²⁺ ions in seawater increases the lifetime by 3–5 times compared to water. The effect of OH⁻ on the oxidation of Fe(II) in water and seawater shows a second degree dependence from 5 to 45°C. The effect of salinity on the oxidation of Fe(II) was found to be independent of temperature, while the effect of temperature was found to be independent of salinity. The energy of activation for the overall rate constant was found to be 7 ± 0.5 kcal mol⁻¹.The effect of pH, temperature, salinity and ionic composition on the oxidation of Cu(I) has also been examined. In NaCl solutions from 0.5 to 6 M, the log k for the oxidation was a linear function of pH (6–8) with a slope of 0.2 ± 0.05. The reaction was strongly dependent on the Cl⁻ concentration with variation of from 0.3 to 340 min from 0.5 to 6 M Cl⁻. The rates of oxidation of Cu⁺ and CuCl⁰ responsible for these effects are dependent upon ionic strength. The energy of activation for the reaction was 8.5–9.9 kcal mol⁻¹ from 0.5 to 6 M. Studies of the oxidation in various NaX salts (X = I⁻, Br⁻ and Cl⁻) give rates in the order Cl⁻ > Br⁻ > I⁻ as expected, due to complex formation of Cu⁺ with X⁻.     

Influence of m-cresol purple indicator additions on the pH of seawater samples: correction factors evaluated from a chemical speciation model

The perturbation of the indicator m-cresol purple on the pH in seawater is illustrated in diagrams, representing measurements in 1-cm and 5-cm cells. The diagrams apply to a measured pH interval of 7.4–8.4 using a 2-mM stock solution of m-cresol purple sodium salt dissolved in seawater. The magnitude of the perturbation is described as correction values, i.e., the change in seawater pH caused by the indicator. The diagrams are based on calculations made by using the equilibrium speciation programme, MARINHALT. From these calculations, and least squares fitting methods, pH correction values are described in terms of the pH difference between each seawater sample and the pH of an indicator stock solution. Calculations are performed for a typical high latitude water and a north Pacific deep water. Diagrams are presented for a salinity of 35 and a temperature of 15°C. Responses to salinities between 32 and 36 and temperatures 15–25°C are illustrated as well. A ±0.05 pH difference between a seawater sample and an indicator stock solution gives a correction of less than 0.001 pH unit for a 1-cm cell. For a 5-cm cell, pH differences between the indicator stock solution and a seawater sample as large as ±0.3 cause corrections smaller than ±0.001 pH unit. Calculations demonstrate that the five-fold lower indicator concentration used with 5-cm cells decreases the perturbation effect by approximately a factor of five relative to 1-cm cells.     

Distribution coefficient of Mg ions between calcite and solution at 10–50°C

The distribution coefficient (λ_Mg) of Mg²⁺ ions between calcite and solution was found to be 0.012 ± 0.001 (10°C), 0.014 ± 0.001 (15°C), 0.019 ± 0.001 (25°C), 0.024 ± 0.001 (30°C), 0.027 ± 0.001 (35°C) and 0.040 + 0.003 (50°C). This indicates a remarkable dependence on temperature. The effect of the Mg²⁺/Ca²⁺ molar ratio in a parent solution on λ_Mg for calcite is small, where the molar ratio lies in the range 0.04-2. However, the λ_Mg value for aragonite tends to decrease with increasing Mg²⁺/Ca²⁺ ratio in the parent solution. The largest Mg content of calcite in the Ca(HCO₃)₂-Mg²⁺ → calcite system is around 2 mol% in the temperature range 10–50°C. Neither homogeneous nor heterogeneous distribution laws hold for aragonite precipitation, and the temperature effect on the coprecipitation of Mg²⁺ ions with aragonite is very small.     

A note on the Japan Sea Proper Water

The water under the main thermocline in the Japan Sea is a single water mass referred to as the Japan Sea Proper Water. It can be defined as having temperature below 2.0°C, salinity above 34.00%, and dissolved oxygen below 7.0 ml 1⁻¹. In the north most of the water above the potential temperature 0.1°C depth (about 800–1000 m) is a mode water, with σ_θ of 27.32 to 27.34 kg m⁻³. North of 40°N it has high oxygen (more than 6.00 ml 1⁻¹) with a distinct discontinuity (oxygen-cline) at the bottom of the mode water. The most probable region for the formation of the water is the area north of 41°N between 132° and 134°E. The deeper water probably is formed in the norther area of 43°N, and directly fills the main part of the Japan Basin north of 41°N and east of 134°E.     

Rates of oxygen transfer from air bubbles to aqueous NaCl solutions at various temperatures

Experiments have been conducted to investigate the effects of temperature on the interfacial surface area and on the rate of oxygen transfer from air bubbles dispersed in aqueous NaCl solutions. Tests were also conducted to estimate the effects of salt concentration on the size of the bubbles. In addition to NaCl solutions, seawater was used in some tests. The temperature effects were investigated at 5, 10, 15, 20, 25, and 30°C. The results showed a pronounced effect of the salt on the size of the bubbles, which first decreased sharply with increasing concentration, but showed no further drop when the concentration was increased beyond 0.6 M. Both in seawater and in the 0.6 M solution, the mass transfer rate, K_LA, increased almost linearly when temperature was increased within the range from 5 to 25°C. The salt solution, as well as the seawater, showed an increase of K_LA of 60–70% over that in pure water at the same temperatures. This effect was the result of increased surface area of bubbles because of decreased coalescence. The increase in surface area was strongly temperature dependent, especially between 15 and 20°C. Contrary to this behavior the surface area in pure water showed, practically, no temperature dependence. The results are explained and discussed on the basis of ion-water interactions.     

Effect of oil and dispersants on the growth of Mussels

Mussels (Mytilus edulis L.) were exposed to North Sea crude oil, microencapsulated oil and dispersants, singly and in combination, and growth rates measured at 24–48 h intervals.Exposure to microencapsulated pure oil (2·0–2·1 mg litre⁻¹) and to microencapsulated mixtures of oil (2·2−2·5 mg litre^-1+5 % of the different dispersants (FINASOL OSR 5, COREXIT 9527, DISPOLENE 36 S) gave approximately the same reduction in growth rate (80–90%) within 170h.Oil chemically dispersed with DISPOLENE 36 S and a pure oil mechanically dispersed in water were significantly less toxic. In high concentrations (2 mg litre⁻¹) all disperants are toxic, DISPOLENE 36 S ssignificantly more than the others.Mussels exposed for 170 h to microencapsulated oil and to microencapsulated oil dispersant mixtures recovered to control growth within 300 h in clean seawater, while in those given pure oil-in-water suspension, the recovery was slower.It is concluded that the toxicity of oil is mainly related to size and concentration of oil particles, while the effect of 5% dispersants added is negligible.     

Size fractionation and optical properties of colloids in an organic-rich estuary (Thurso, UK)

The optical characteristics of a black water river estuary from the north coast of Scotland were examined in the filtered (0.4 µm), ultrafiltered (5 kDa) and colloid-enriched fractions of estuarine samples. The samples were collected over the full salinity range during a period when the pH was relatively constant (8.2–8.5) throughout the estuary, allowing the influence of salinity on estuarine colloidal processes to be distinguished. The properties examined in the bulk, the low molecular weight (LMW) and the colloidal fraction (HMW) were UV–visible absorption, 3-D fluorescence excitation–emission matrix (EEM) spectrum, inorganic and organic carbon, mean size (by dynamic light scattering), and size distribution by flow field-flow fractionation analysis (FlFFF). The combined results of these analyses support the view that river-borne, humic-rich colloids underwent two types of transformation upon mixing with the seawater end member. The first one resulted in an apparent increase in the abundance of LMW constituents and may be explained by coiling of the individual humic macromolecules. The second one resulted in an increase in the mean size measured in both the lower and higher colloidal size ranges, and may be explained by aggregation of colloids to form entities that were still mostly colloidal i.e., smaller than 0.4 µm. The LMW contribution to the bulk optical properties increased with increasing salinity. Very similar findings were obtained from simulated mixing experiments using a Nordic Reference NOM extract as a source of freshwater colloids. This indicates that changes in the molecular architecture and molar mass of river-borne colloids—not changes in their chemical nature—were responsible for the observed variations in the spectral characteristics of CDOM in this estuary.     

Trace metal fronts in Scottish coastal waters

Dissolved cadmium and copper concentrations have been determined in 76 surface water samples in coastal and ocean waters around Scotland by anodic stripping voltammetry (ASV). A trace metal/salinity ‘front’ is observed to the west, north and north-east of Scotland separating high salinity ocean water (>35 × 10⁻³) with low concentrations of dissolved Cd and Cu from lower salinity (<35 × 10⁻³) coastal water containing higher concentrations of Cd and Cu. Mean Cd concentrations in ocean and coastal waters are 7 ng dm⁻³ (0·06 n ) and 11 ng dm⁻³ (0·10 n ) respectively; for Cu the respective levels are 60 ng dm⁻³ (0·95 n ) and 170 ng dm⁻³ (2·68 n ). The observed distribution is attributed principally to freshwater runoff and the advection of contaminated Irish Sea water into the study area.     

海水电解质pmv的补充测定及其加和性关系的验证

首次用新研制的高精密磁力浮沉子密度计测定ＮａＨＣＯ３，ＫＢｒ，ＫＮＯ３和Ｃａ（ＮＯ３）２在盐度为３０．０和３４．７温度为２９８、１０Ｋ时的偏摩尔体积（即ｐｍｖ）。重新测定了ＮａＣｌ，ＫＣｌ．Ｎａ２ＳＯ４和ＭｇＳＯ４在海水中的ｐｍｖ，并用实验精密验证了海水中主要电解质的ｐｍｖ的加和性关系。     

Determination of Henry's law constants for hexachlorocyclohexanes in distilled water and artificial seawater as a function of temperature

Henry's law constants were determined for α- and γ-hexachlorocyclohexane (HCH) as a function of temperature (0.5–45°C) in artificial seawater (SW; 30‰) and distilled water (DW) using the gas stripping method. Water samples (1–5 ml) were withdrawn from the stripping vessel during the stripping process (30–360 h), solvent extracted and analyzed by gas chromatography—electron-capture detection. The effect of bubbling depth was checked to ensure that bubbles leaving the system were at equilibrium with HCHs in the aqueous phase. Henry's law constants determined at 35 and 45°C in SW were significantly higher (P≤ 0.05) than in DW for both α- and γ-HCH, but not at lower temperatures. The slopes (m) and intercepts (b) of log H vs. 1 / T plots were: α-HCH (DW, 0.5–45°C); m = −2810 ± 110, B = 9.31 ± 0.38; α-HCH (SW, 0.5–23°C); M = −2969 ± 218, B = 9.88 ± 0.76; γ-HCH (DW, 0.5–45°C); M = −2382 ± 160, B = 7.54 ± 0.54; γ-HCH (SW, 0.5–23°C); M = −2703 ± 276, B = 8.68 ± 0.96. Henry's law constants determined in this study compared well with those calculated from reported vapor pressure and solubility data.     

The oxygen isotope composition of water masses in the northern North Atlantic

The ratio of oxygen-18 to oxygen-16 (expressed as per mille deviations from Vienna Standard Mean Ocean Water, δ¹⁸O) is reported for seawater samples collected from seven full-depth CTD casts in the northern North Atlantic between 20° and 41°W, 52° and 60°N. Water masses in the study region are distinguished by their δ¹⁸O composition, as are the processes involved in their formation. The isotopically heaviest surface waters occur in the eastern region where values of δ¹⁸O and salinity (S) lie on an evaporation–precipitation line with slope of 0.6 in δ¹⁸O–S space. Surface isotopic values become progressively lighter to the west of the region due to the addition of ¹⁸O-depleted precipitation. This appears to be mainly the meteoric water outflow from the Arctic rather than local precipitation. Surface samples near the southwest of the survey area (close to the Charlie Gibbs Fracture Zone) show a deviation in δ¹⁸O–S space from the precipitation mixing line due to the influence of sea ice meltwater. We speculate that this is the effect of the sea ice meltwater efflux from the Labrador Sea. Subpolar Mode Water (SPMW) is modified en route to the Labrador Sea where it forms Labrador Sea Water (LSW). LSW lies to the right (saline) side of the precipitation mixing line, indicating that there is a positive net sea ice formation from its source waters. We estimate that a sea ice deficit of ≈250 km³ is incorporated annually into LSW. This ice forms further north from the Labrador Sea, but its effect is transferred to the Labrador Sea via, e.g. the East Greenland Current. East Greenland Current waters are relatively fresh due to dilution with a large amount of meteoric water, but also contain waters that have had a significant amount of sea ice formed from them. The Northeast Atlantic Deep Water (NEADW, δ¹⁸O=0.22‰) and Northwest Atlantic Bottom Waters (NWABW, δ¹⁸O=0.13‰) are isotopically distinct reflecting different formation and mixing processes. NEADW lies on the North Atlantic precipitation mixing line in δ¹⁸O–salinity space, whereas NWABW lies between NEADW and LSW on δ¹⁸O–salinity plots. The offset of NWABW relative to the North Atlantic precipitation mixing line is partially due to entrainment of LSW by the Denmark Strait overflow water during its overflow of the Denmark Strait sill. In the eastern basin, lower deep water (LDW, modified Antarctic bottom water) is identified as far north as 55°N. This LDW has δ¹⁸O of 0.13‰, making it quite distinct from NEADW. It is also warmer than NWABW, despite having a similar isotopic composition to this latter water mass.