Diffusion of seawater ions. Part II. The role of activity coefficients and ion pairing

A theoretical evaluation of basic thermodynamic relationships reveals that variation of activity coefficients, ion pairing and electrical interactions must be considered when modelling ionic diffusion in seawater. The contributions of ion-pair formation and change in activity coefficient along the diffusion path were studied experimentally by conducting diffusion experiments in which solutions of KCl, NaCl, MgCl₂, Li₂SO₄, K₂SO₄, Na₂SO₄ and MgSO₄, at an ionic strength of 0.7, were allowed to diffuse into distilled water. The study reveals that the thermodynamic factor, required to correct for changes in the activity coefficient along the diffusion path, is significant for all the salts studied. Agreement between a simple diffusion model, which does not include ion pairing, and observed data was good for completely dissociated salts, but poor for salts which are known to form ion pairs at the concentration levels studied. The diffusion of MgSO₄, 0.425 of which is associated at I = 0.7, was successfully modelled by assuming that the diffusion coefficient of the MgSO₄⁰ ion pair is different from the diffusion coefficient of the dissociated salt. The diffusion coefficient of this ion pair is estimated to be 1.9 × 10⁻⁵ cm² s⁻¹ at 30°C, as compared to 0.49 × 10⁻⁵ cm² s⁻¹ for the dissociated salt. It is suggested that the high mobility of this ion pair could cause magnesium enrichment in pore water of sulfate depleted sediments.     

Stability of ion pairs from gypsum solubility degree of ion pair formation between the major constituents of seawater

The stability constants of the ion pairs NaSO₄^?, KSO₄^?, MgSO₄^?, CaSO₄, MgCl⁺ and CaCl⁺ were determined at 25°C and 0.7 M formal ionic strength, by measuring the solubility of gypsum (CaSO₄ · 2H₂O) in different media. The media used contained one or two of the following electrolytes: NaCl, KCl, MgCl₂, NaClO₄, Mg(ClO₄)₂, Na₂SO₄. Values for the stability constants are 1.22, 1.84, 12.3, 30.6, 0.48 and 1.20 M^?1, respectively, and the solubility product for gypsum is 2.87 · 10^?4M². The distribution of the main constituents of seawater was calculated using these results and the values of the carbonate and bicarbonate constants given by Dyrssen and Hansson (1972–1973). The solubility of gypsum in seawater as calculated and determined experimentally was 21.43 mM and 21.10 mM, respectively.     

Ion association of chloride and sulphate with sodium,potassium, magnesium and calcium in seawater at 25°C

Stoichiometric association constants, which have been measured for the ion pairs of Cl^? and SO₄^?2 with Na⁺, K⁺, Mg²⁺, and Ca²⁺, were used to determine the speciation in an artificial sea water containing only these ions. The resulting distribution is quite different to that found in earlier models in which chloride ion association was ignored. The concentrations of chloride ion pairs with the cations are 4 to 5 times larger than the concentrations of the sulphate ion pairs with the same cations. The total activity coefficients of the neutral salts in sea water calculated from the model are in good agreement with the experimentally measured values. The concentration of MgSO₄⁰ calculated to be present agrees with the amount determined from ultrasonic absorption data. The calculated solubility of gypsum is also in good agreement with the measured values.     

Seawater: an explanation of differential isothermal compressibility measurements in terms of hydration and ion-water interactions

Hydration, ion-water interactions, and water structure effects in seawater were studied by determining differences (Δβ) between the compressibilities of test salt solutions and the compressibilities of reference solutions. The reference solutions were distilled water and seawater (35%0), and the test salt solutions were either 0.13 m or 0.26m with respect to one of the following test salts: LiCl, NaCl, KCl, CsCl, NaF, NaI, MgCl₂, CaCl₂, BaCl₂, Na₂SO₄, K₂SO₄, and MgSO₄. The compressibility measurements (to 900 bars) were carried out at 2°C and also at 15°C using a differential method in which a pressure increase or a temperature increase causes Δβ to become less negative. At 1 bar and 15°C, the Δβ (0.26 m, distilled water reference) values ranged from ?1.14 × 10^?6 bar^? for NaI to ?3.84 × 10^?6 bar^?1 for Na₂SO₄, and the Δβ (0.26 m, seawater reference) values ranged from ?1.30 × 10^?6 bar^?1 for NaCl to ?3.04 × 10^?6 bar^?1 for Na₂SO₄. The Δβ values were used to calculate hydration numbers. Entropy of transfer, excess hydrogen bond breaking (determined by NMR), and effective radii of ions are properties which can be used to describe the influence of ions on water structure. The extent to which these properties correlate with Δβ values depends upon whether the ion is an anion or a cation, and this correlation forms the thesis that anions alter water structure in a different way than do cations.     

Stability constants of NaSO4−, MgSO4, MgF+, MgCl+ ion pairs at the ionic strength of seawater by potentiometry

The stability of the ion pair NaSO₄ was determined by measuring the change in sodium activity with medium composition at constant ionic strength, using a sodium-sensitive glass electrode. The stability constants of MgSO₄ and MgCl⁺ were determined indirectly from measurements of the stability of MgF⁺ in different media. All measurements were performed at 1 atm pressure, 25 ± 0.1 °C and 0.7 M formal ionic strength. The stability constants for NaSO₄^?, MgSO₄, MgF⁺ and MgCl⁺ are 1.8 ± 0.1, 6.3 ± 0.1, 22.9 ± 0.1 and 0.34 ± 0.02 M^?1, respectively.     

Calorimetric study of the thermodynamics of formation of MgSO4 and NaSO4− ion pairs at the ionic strength of seawater

The formation of the ion pairs MgSO₄ and NaSO₄^? was investigated calorimetrically at 0.75 M ionic strength, 25°C, 1 atm. Simultaneous determinations of enthalpy changes, ΔH₁⁰, and stability constants, K₁, were not possible, and values of K₁ determined independently had to be introduced for the calculation of ΔH₁⁰. The values of ΔH₁⁰ obtained were 1–3 kJ mol^?1 for MgSO₄ and 0 kJ mol^?1 for NaSO₄^?.     

Sulphate complexation in seawater: A relation between the stability constants of sodium sulphate and magnesium sulphate in seawater from a determination of the stability constant of hydrogen sulphate and a calculation of the single ion activity coefficient of sulphate

The conditional stability constant of HSO₄^? has been determined at 25°C, 1 atm and a formal ionic strength of 0.7 M in solutions containing sodium, magnesium, chloride and sulphate. This was done spectrophotometrically (UV), using diphenylamine as indicator. The value obtained was 17.0 ± 0.1 (molar scale). Single ion activity coefficients for Na₂SO₄, K₂SO₄ and MgSO₄ have been calculated according to the Bates et al. (1970) model, assuming that the sulphate ion is not hydrated. It was found that the single ion activity coefficient of sulphate changes very little between Na₂SO₄, K₂SO₄ and MgSO₄ when the formal ionic strength is kept constant.These results have been used to obtain relations between the stability constants of NaSO₄^? and MgSO₄ valid for seawater.     

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

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.     

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.     

Specific absorption coefficient and phytoplankton community structure in the southern region of the California Current during January 2002

Measurements of the specific absorption coefficients of phytoplankton (a*_ph) are currently required to estimate primary productivity at regional to global scales using satellite imagery. The variability in a*_ph and phytoplankton size fraction was determined during January 2002 in the southern region of the California Current. Median values of a*_ph at 440 nm and 674 nm were 0.061 and 0.028 m² (mg Chl-a)^?1 and significant variability was found between inshore and offshore stations. A decrease of a*_ph is associated with increased phytoplankton abundance and larger species. The a*_ph tends to be high when the photoprotector zeaxanthin is present in elevated concentrations and phytoplankton abundance lower. The nano-microphytoplankton (>5 µm) community consisted of 28 diatom and 15 dinoflagellate genera with mean abundance values of 2.8 and 1.6 × 10³ cells l^?1, respectively. The picophytoplankton (<5 µm) community consisted of Prochlorococcus sp. (mean 8.2 × 10⁶ cells l^?1) and Synechococcus sp. (mean 19.5 × 10⁶ cells l^?1), as well as a mixture of picoeukaryotes (mean 8.6 × 10⁶ cells l^?1). The contributions of nano-microphytoplankton and picophytoplankton to the total biomass (µg C l^?1) were 46% and 54%, respectively. This study showed that picophytoplankton cells increased 2.5 times up during January 2002 compared with the previous year. It was concluded that the waning of La Niña conditions had a clear effect on the pelagic ecosystem in January 2002 and that the higher microphytoplankton abundance in the California Current was dominated by local and regional seasonal processes.     

Methane flux dynamics in relation to methanogenic and methanotrophic populations in the soil of Indian Sundarban mangroves

The dynamics of methane (CH₄) flux in relation to populations of methanogenic and methanotrophic bacteria was studied under the different biophysical conditions of the Indian Sundarban mangrove ecosystem. Soil depth profile analysis (up to 60 cm) in the lower littoral zone (LLZ) revealed that a methanogenic population of 6.45 ± 0.19 × 10⁴ cells/g dry weight (dry wt) of soil accounted for a CH₄ production rate of 6.23 ± 3.53 × 10³ µmol m^?2 day^?1, whereas in the surface soil, a methanogenic population of 3.34 ± 0.37 × 10⁴ cells/g dry wt of soil accounted for a CH₄ production rate of 31.6 ± 0.57 µmol m^?2 day^?1. The CH₄ oxidation rate at 60 cm depth in the LLZ was 24.42 ± 1.28 µmol m^?2 day^?1, with an average methanotrophic population of 1.33 ± 0.43 × 10⁴ cells/g dry wt of soil, whereas in the surface soil, the oxidation rate and average population were 3.38 ± 1.43 × 10³ µmol m^?2 day^?1 and 12.80 ± 2.54 × 10⁴ cells/g dry wt of soil, respectively. A similar soil profile in terms of CH₄ dynamics and the populations of methanogenic and methanotrophic bacteria was found in the mid‐littoral and upper littoral zones of the studied area. The results demonstrate that most of the produced CH₄ (approximately 60%) was oxidized by methanotrophic bacteria present in the soil, thus revealing their principal role in regulating the CH₄ flux from this unique ecosystem.     

Ionic medium effects in sea water — A comparison of acidity constants of carbonic acid and boric acid in sodium chloride and synthetic sea water

It is shown that the values of pK_1C and pK_2C for carbonic acid, pK_B for boric acid and the ionic product of water, pK_w, in sea water may be explained on the basis of their determination in 0.7 M_w sodium chloride and the formation of the following ion-pairs: NaSO₄^?, MgSO₄, CaSO₄, MgCO₃, CaCO₃, MgHCO₃⁺, CaHCO₃⁺, MgOH⁺, HSO₄^?, MgB(OH)₄⁺ and CaB(OH)₄⁺. On the whole the calculated stability constants are lower than those given by Garrels and Thompson (1962).     

Anionic species of V,As, Se,Mo, Sb,Te and W in the Scheldt and Rhine estuaries and the Southern Bight (North Sea)

Oxy-anionic species of V, As, Se, Mo, Sb, Te and W were measured in solution and suspension in samples obtained during several cruises in the Dutch Wadden Sea, the offshore region of the Southern Bight (North Sea) and in the estuaries of the Rhine and Scheldt. Dissolved concentrations at salinities above 34·5 × 10^?3 ( = 34·5%. S) agreed generally well with published open ocean values. It is suggested that Se speciation differs from the open ocean.In the Wadden Sea, concentrations of V, Se, Mo and Sb were linearly related to salinity (10–35 × 10^?3). The good agreement between measured and extrapolated values at a salinity of 0·5 × 10^?3 suggests conservative behaviour in the Rhine estuary (with residence time of freshwater in the order of a few days).Dissolved concentration vs. salinity plots in the Scheldt estuary (residence time 2–3 months) showed pronounced minima and maxima. These occurred in the low or medium salinity range for V, As and Sb. Linear behaviour was observed for Se and Mo (in some cases, relatively large differences between cruises were detected). Deviations from linearity in the plots are interpreted in terms of thermodynamic equilibrium conditions involving species with different solubilities (V), local input from land (As, Se, Sb, Te) and removal from solution (As), probably through coprecipitation with Fe(OH)₃.In the offshore samples, the contributions of particulate forms to the total element concentrations were small (<15%). At higher SPM concentrations (about 30 mg dm^?3), this percentage remained small for Se, Mo and Sb (<15%); it was substantial for V and As (25–50%).     

Acute response versus reproductive performance in five strains of brine shrimp exposed to copper sulphate

Five geographically and genetically diverse strains of the brine shrimp, Artemia salina, were tested for response to copper sulphate. Mean survival times (MST) were determined for each strain following continuous exposure to concentrations of 10^?1, 1, 10¹, 10², 10³, 10⁴ and 10⁵ ppm CuSO₄. In addition, lifetime reproductive performance parameters were evaluated for 15 females from each strain after 24 h exposure to 0·067 × 10^?9 CuSO₄.Two-factorial ANOVA revealed that treated females produced fewer offspring per brood and fewer broods per female, resulting in an overall decline in the mean number of offspring per day per female over the reproductive span. When the standard 24 h MST results are compared with the 24 h dose level of CuSO₄ found to impair reproductive performance, the latter was from 24,000 to 156,000 times more sensitive, depending upon strain.     

Stability of the calcium sulphate ion pair at the ionic strength of seawater by potentiometry

The stability of the ion pair CaSO₄ was determined from measurement of the change in calcium ion activity with medium composition at constant ionic strength. A calcium selective PVC-matrix liquid membrane electrode was used to monitor the calcium ion activity. All measurements were performed at 1 atm, 25 ± 0.1°C and 0.7 M formal ionic strength. The evaluation of the stability constant depends on the degree of complexation between calcium and chloride and between sodium and sulphate. The dependence of K_CaSO4, on K_NaSO4 and K_CaCl can be described by the following relations:K_CaSO4=17.7 K_CaCl+16.5 (K_NaSO4=1.8)K_CaSO4=18.8 K_CaCl+17.3 (K_NaSO4=2) for K_CaCl=0–1A value of K_CaSO4=25.4 is suggested.     

Determination of the zinc complexing capacity in seawater by cathodic stripping voltammetry of zinc—APDC complex ions

A novel technique to determine complexing capacities for zinc is presented. The free zinc concentration is determined by cathodic stripping voltammetry preceded by adsorptive collection of complexes of zinc with ammonium pyrrolidine dithiocarbamate (APDC). The reduction peak of zinc is depressed as a result of ligand competition by natural organic material in the sample. Sufficient time is allowed to reach equilibrium between this material and added APDC, and equilibrium is maintained during the measurement. Both electrochemically reversible and irreversible complexes can therefore be investigated. Values for K_ZnAPDC^′ are calibrated against NTA and EDTA in seawater of several salinities; log K_ZnAPDC^′ was found to be 4.40 at 36‰, 4.36 at 24‰, 4.43 at 12‰, and 4.87 at 2.3‰. The ligand concentration and conditional stability constant, K_ZnL^′, for complexing ligands in a sample from the Irish Sea were determined in the presence of 4 × 10^?5 M APDC and with added zinc concentrations between 5 × 10^?9 and 3 × 10^?7 M. The data best fitted a complexation model containing two ligands with concentrations of 2.6 and 6.2 and 10^?8 M, and with values for log K_ZnL^′ of 8.4 and 7.5, respectively. These results are comparable to those obtained with other equilibrium techniques, but the values of the constants are greater than those from ASV measurements.     

The interaction of Np(V)O2+ with common mineral surfaces in dilute aqueous solutions and seawater

The extent and kinetics of Np(V)O₂⁺ adsorption from dilute aqueous solutions and seawater onto a variety of synthetic and natural solids were determined at 25°C and 1 atm total pressure. Extensive and complex adsorption reactions were found, contrary to speculations in the literature that NpO₂⁺ should behave as a simple monovalent ion with a low affinity for surfaces. When normalized to adsorption per unit solid surface area, the ranking for the synthetic solids was aragonite ? calcite > goethite ? MnO₂ ≈ clays. Natural materials generally followed the same behavior patterns as their synthetic counterparts. The dissolved/adsorbed ratio was found to be constant over a wide range (10^?13–10^?7M) of NpO₂⁺ concentrations. At higher concentrations the extent of adsorption decreased until a solubility limit was reached at approximately 10^?5 M.Solution composition had the most significant influence for NpO₂⁺ adsorption on goethite, where much more extensive adsorption occurs in dilute solutions than in seawater. When seawater is added to a dilute solution, extensive desorption of NpO₂⁺ from goethite occurs. Tests conducted on NpO₂⁺ adsorbed on carbonates indicated that it remained in the V oxidation state.There is a growing consensus that Pu dissolved in natural waters also occurs dominantly in the V oxidation state as PuO₂⁺ ion. Consequently, these results for NpO₂⁺ may serve as a guide for Pu behavior when also in the V oxidation state. The fact that most adsorbed Pu is found in the III or IV oxidation states indicates that reduction of Pu may occur subsequent to adsorption in the V oxidation state.     

A case study of sewage discharge in the shallow coastal area of the Northern Adriatic Sea (Gulf of Trieste)

A case study was carried out in 2000 in the shallow coastal area of the Northern Adriatic Sea (Gulf of Trieste) where untreated domestic sewage and industrial wastes are discharged at rate of 5500 m³·day^?1. The sewage plume above the outfall was followed using faecal coliforms (FC) and overturning length scale (l_T). The latter was rejected as a marker as the discharge conditions prohibit following the turbulence of sewage water. Intermittent sewage discharge is reflected in the minimal effect of eutrophication. Increase of phytoplankton biomass is thus only minor compared with the unpolluted area regardless of elevated concentrations of sewage‐derived nutrients (confirmed by correlation coefficients between FC and NH₄⁺, TP, PO₄^3?: 0.78, 0.71 and 0.67, respectively). Deteriorated trophic status, determined by the TRIX index, was observed only in the surface layer (average TRIX: 5.67). High FC content well above the regulation limit (up to 2.6 × 10⁵ FC·100 ml^?1) represents, therefore, the major negative impact of the improperly treated waste for the risk to human health.     

Bacterial populations,heterotrophic potentials,and water quality in three New Zealand Rivers

Abstract

Thirty sites were sampled in three New Zealand rivers (Waikato, Maitai, and Wakapuaka) during late summer 1977. Samples were collected from just below the surface at mid river or in the tailraces below hydro‐electric dams.

Parameters measured included bacterial numbers (direct counts), heterotrophic potential (V_max ), adenosine triphosphate (ATP), chlorophyll a (Chi a), and concentrations of nitrogen and phosphorus compounds.

Bacterial populations per millilitre fluctuated threefold (6.4–19.4 × 10⁵) along the Waikato River and were lower and more consistent in the two South Island rivers (1.46–2.55 × 10⁵). In contrast, V_max varied 5000‐fold in the Waikato River, from a characteristically oligotrophic value of 0.0035 μg. l^?1·h^?1 (Lake Taupo outlet) to a eutrophic value of 18.4 μg. l^?1·h^?1 at the Mihi bridge. V_max for the two South Island rivers ranged from 0.0091 to 0.189 μg. l^?1 · h^?1.

ATP, Chi a, Kjeldahl nitrogen, nitrate nitrogen, and total phosphorus concentrations for the 20 sites on the Waikato River varied in a similar way to the V_max and bacterial data. There were large peaks at the Mihi bridge, lower values for the dam tailraces and significant increases for the sites below Hamilton. Concentrations for these parameters were lower and more consistent along the lengths of the two South Island rivers.

Most parameters were significantly correlated with each other for the Waikato River samples. The strongest correlations were between V_max and bacterial numbers and between V_max and nitrate nitrogen. In the Maitai and Wakapuaka River series these correlations were also significant, but the only other significant correlations recorded there were between ATP and nitrate nitrogen, and between ATP and bacterial numbers.