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1.
The interactions of Fe(II) and Fe(III) with the inorganic anions of natural waters have been examined using the specific interaction and ion pairing models. The specific interaction model as formulated by Pitzer is used to examine the interactions of the major components (Na+, Mg2+, Ca2+, K+, Sr2+, Cl−, SO4−, HCO3−, Br−, CO32−, B(OH)4−, B(OH)3 and CO2) of seawater and the ion pairing model is used to account for the strong interaction of Fe(II) and Fe(III) with major and minor ligands (Cl−, SO42−, OH−, HCO3−, CO32− and HS−) in the waters. The model can be used to estimate the activity and speciation of iron in natural waters as a function of composition (major sea salts) and ionic strength (0 to 3 M). The measured stability constants (KFeX*) of Fe(II) and Fe(III) have been used to estimate the thermodynamic constants (KFeX) and the activity coefficient of iron complexes (γFeX) with a number of inorganic ligands in NaClO4 medium at various ionic strengths: In(KFeX/γFeγX) = InKFeX − In(γFeX) The activity coefficients for free ions (γFe, γx) needed for this extrapolation have been estimated from the Pitzer equations. The activity coefficients of the ion pairs have been used to determine Pitzer parameters (BFeX, BFeX0, CFeXφ) for the iron complexes. These results make it possible to estimate the stability constants for the formation of Fe(II) and Fe(III) complexes over a wide range of ionic strengths and in different media. The model has been used to determine the solubility of Fe(III) in seawater as a function of pH. The results are in good agreement with the measurements of Byrne and Kester and Kuma et al. When the formation of Fe organic complexes is considered, the solubility of Fe(III) in seawater is increased by about 25%. 相似文献
2.
3.
Kenneth S Johnson 《Marine Chemistry》1982,11(3):285-286
Recently, the stoichiometric association constant for MgSO4o 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 MgSO4o ion pair. 相似文献
4.
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. 相似文献
5.
Kenneth S. Johnson 《Marine Chemistry》1981,10(3):195-208
It is shown that the values of the diffusion coefficient of MgSO40 ion pairs computed by Harned and Hudson (J. Am. Chem. Soc., 73: 5880, 1951) and Katz and Ben-Yaakov (Mar. Chem., 8: 263, 1980) are too high by a factor of 2. The correct value of the ion pair diffusion coefficient at infinite dilution was obtained from the measured mutual diffusion coefficient after applying corrections for incomplete dissociation, the electrophoretic effect, the viscosity of the solution and the effect of chloride ion pairs (in the ionic media used during measurements of the stoichiometric association constant of MgSO40 ion pairs). The MgSO40 diffusion coefficient is calculated to be 0.65 × 10?5 cm28?1. The result is independent of the concentration up to a value of 0.8 mol dm?3.Values were also calculated for the diffusion coefficients of the following ion pairs: NaSO4? (0.81 × 10?5), CaCl+ (0.78 × 10?5), BaCl+ (0.85 × 10?5), NaCl0 (0.86 × 10?5), KCl0 (1.09 × 10?5), NH4Cl0 (1.10 × 10?5) and CaCl0 (1.27 × 10?5). In general, the diffusion coefficients are less than those of the free ions. The results show quantitative agreement with theoretical predictions. 相似文献
6.
A liquid-liquid partition, ligand exchange procedure involving the formation of copper(II) complexes with acetylacetone is presented for the determination of stability constants and concentrations of copper chelators in seawater. Acetylacetone competes with natural ligands for copper, and the equilibrium concentration of the copper acetylacetonate complex is used in speciation calculations. The concentration of the complex is calculated by partitioning a fraction of it into an organic phase and determining the total Cu concentration in that phase by back extracting with acid, and analyzing by flameless atomic absorption spectroscopy. The concentration of Cu acetylacetonate in seawater in equilibrium with the organic phase is calculated from the partition coefficient. The simple, thermodynamically well characterized procedure offers several advantages over previous techniques. Studies using organic free seawater and model ligands show good agreement between experimental and calculated conditional stability constants. Studies from seawater in Biscayne Bay, Florida, indicate two ligand types are present; type 1, K1 = 1.2 × 1012, CL1 = 5.1 × 10−9 M; type 2, K2 = 2.8 × 1010, CL2 = 1.1 × 10−7 M. Speciation is dominated by ligand type 1. Depth profiles of [Cu(II)]free/[Cu(II)]total measured with the procedure at ambient copper concentrations show an increase from < 5 × 10−5 at 50–60 m to > 1 × 10−3 at the surface at two stations off the Florida coast. 相似文献
7.
Frederick L. Sayles 《Marine Chemistry》1980,9(4):223-235
Analyses of the concentration product (Ca2+) × (CO32−) in the pore waters of marine sediments have been used to estimate the apparent solubility products of sedimentary calcite (K′SPc) and aragonite (K′SPa) in seawater. Regression of the data gives the relation In K′PSPc = 1.94 × 10−3 δP − 14.59 The 2°C, 1 atm value of K′SPc is, then, 4.61 × 10−7 mol2 l−2. The pressure coefficient yields a
at 2°C of −43.8 cm3 atm−1. A single station where aragonite is present in the sediments gives a value of K′SPa = 9.2 × 10−7 (4°C, 81 atm). The calcite data are very similar to those determined experimentally by Ingle et al. (1973) for K′SPc at 2°C and 1 atm. The calculated
is also indistinguishable from the experimental results of Ingle (1975) if
is assumed to be independent of pressure. 相似文献
8.
A batch sorption technique for the determination of particle–water interactions of hydrophobic organic micropollutants under simulated estuarine conditions is described. Results are presented for the behaviour of 2,2′,5,5′-tetrachlorobiphenyl (2,2′,5,5′-TCB) in river and sea waters, both in the presence and absence of estuarine suspended particles. Adsorption onto particles in sea water was enhanced compared with adsorption in river water owing to salting out of the compound, and possibly of the particulate organic matter, in the presence of high concentrations of dissolved ions. The particle–water distribution coefficient, KD, decreased from about 120×103 to 10×103 ml g−1, and from about 150×103 to 20×103 ml g−1, in river water and sea water, respectively, over a particle concentration range of 10–1000 mg l−1. Incomplete recovery of compound from the reactor walls is partly responsible for a particle concentration effect, while artefacts relating to inadequate sediment and water phase separation were ruled out following further experiments. The particle concentration effect, which is replicated in many field studies of hydrophobic organic micropollutants, including 2,2′,5,5′-TCB, is incorporated into a simple partitioning model and is discussed in the context of the likely estuarine behaviour of such compounds. 相似文献
9.
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. 相似文献
10.
Francesco Crea Alba Giacalone Antonio Gianguzza Daniela Piazzese Silvio Sammartano 《Marine Chemistry》2006,99(1-4):93
In this paper SIT and Pitzer models are used for the first time to describe the interactions of natural and synthetic polyelectrolytes in natural waters. Measurements were made potentiometrically at 25 °C in single electrolyte media, such as Et4NI and NaCl (for fulvic acid 0.1 < I /mol L− 1 < 0.75), and in a multi-component medium simulating the composition of natural waters at a wide range of salinities (for fulvic and alginic acids: 5 < S < 45) with particular reference to sea water [Synthetic Sea Water for Equilibrium studies, SSWE]. In order to simplify calculations, SSWE was considered to be a “single salt” BA, with cation B and anion A representing all the major cations (Na+, K+, Mg2+, Ca2+) and anions (Cl−, SO42−) in natural sea water, respectively. The ion pair formation model was also applied to fulvate and alginate in artificial sea water by examining the interaction of polyanions with the single sea water cation. Results were compared with those obtained from previous speciation studies of synthetic polyelectrolytes (polyacrylic and polymethacrylic acids of different molecular weights). Results indicate that the SIT, Pitzer and Ion Pairing formation models used in studies of low molecular weight electrolytes may also be applied to polyelctrolytes with a few simple adjustments. 相似文献
11.
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. 相似文献
12.
Pasquale Crea Concetta De Stefano Demetrio Milea Silvio Sammartano 《Marine Chemistry》2008,112(3-4):142-148
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 Xstat = 0.60), and log X213 = 6.11 and log X214 = 2.15 for Mg2CaH3Phy3− and Mg2CaH4Phy2− (log Xstat = 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). 相似文献
13.
This paper presents a parameterized model for the particulate and dissolved manganese profiles in two stratified fjords. Rates of oxidation and reduction of manganese are of the order of 1.0 × 10−15 mol cm−3 s−1. Oxidation of manganese is probably not promoted by an inorganic surface-catalyzed reaction. Cycling of manganese in the redoxcline is extensive (10–100 cycles) and is related to the input of manganese to the fjords. Calibration of the model against sediment-trap-data allow instantaneous eddy diffusion coefficients to be estimated. These are of the order of 0.01 and 1.0 × 10−4 cm2 s−1. 相似文献
14.
Dissolved Al carried in river water apparently undergoes a fractional removal at the early stages of mixing in the Conway estuary. On the other hand, dissolved Al behaves almost conservatively in high salinity (>13) estuarine waters. In order to understand the geochemistry of Al in these estuarine waters, simple empirical sorption models have been used. Partitioning of Al occurs between solid and solution phases with a distribution coefficient, Kd, which varies from 0.67 × 105 to 3.38 × 106 ml g−1 for suspended particle concentrations of 2–64 mg l−1. The Kd values in general decrease with increasing suspended particulate matter and this tendency termed the “particle concentration effect” is quite pronounced in these waters. The sorption model derived by previous workers for predicting concentrations of dissolved Al with changing suspended sediment loads has been applied to these data. Reasonable fits are obtained for Kd values of 105, 106 and 107 ml g−1 with various values of α. Further, a sorption model is proposed for particulate Al concentrations in these waters that fits the data extremely well defined by a zone with Kd value 107 ml g−1 and C0 values 16 × 10−6 mg ml−1 and 92 × 10−6 mg ml−1. These observations provide strong evidence of sorption processes as key mechanisms influencing the distribution of dissolved and particulate Al in the Conway estuary and present new insight into Al geochemistry in estuaries. 相似文献
15.
Shear and Richardson number in a mode-water eddy 总被引：1，自引：0，他引：1
Measurements of stratification and shear were carried out as part of the EDDIES tracer release experiment in mode-water eddy A4 during the summer of 2005. These measurements were accomplished using both shipboard instrumentation and a drifting mooring. A strong relationship between shear intensity and distance from the center of the eddy A4 was observed with the shipboard ADCP. Diapycnal diffusivity at the SF6 tracer isopycnal prior to and during the release was estimated from the drifting mooring to be 2.9×10−6 m2 s−1. Diffusivity increased by an order of magnitude to 3.2×10−5 m2 s−1 during the period of the final tracer survey in early September, which was similar to the value estimated from the tracer analysis for the whole experiment (3.5×10−5 m2 s−1, [Ledwell, J.R., McGillicuddy Jr., D.J., Anderson, L.A., 2008. Nutrient flux into an intense deep chlorophyll layer in a mode-water eddy. Deep-Sea Research II, this issue [doi:10.1016/j.dsr2.2008.02.005]]. 相似文献
16.
Alfredo Seritti David Pellegrini Elisabetta Morelli Corrado Barghigiani Romano Ferrara 《Marine Chemistry》1986,18(2-4)
Copper complexing capacity of cell exudates of Dunaliella salina in natural seawater culture medium was investigated in order to evaluate the influence of this organism on speciation of trace metals in seawater.Seawater samples were collected at 200 m and 2 miles off the coast and immediately filtered. Copper complexing capacity (CCCu) and stability constants (K′) of related cupric complexes were then measured. They were, respectively, 27.1 × 10−8 mol l−1 and 0.56 × 107 l mol−1 for the samples collected at 200 m and 12.8 × 10−8 mol l−1 and 6.10 × 107 l mol−1 for those collected 2 miles off the coast. A stock culture (20 ml, 106 cells ml−1) in log-phase was inoculated in 2 l of each sample of filtered natural seawater. The trend of cell influence was estimated on filtered culture medium by measuring CCCu and K′ after 1 h, 3 and 7 days. From the results it appears that CCCu increased with respect to time and this was related to the growth rate, indicating a certain relationship with cell metabolic activity.It can be concluded that a comparison between the culture referring to 200 m and 2 miles, respectively, shows that the former presents a CCCu two times higher than the latter while the K′ is ten times higher at 2 miles than that at 200 m. 相似文献
17.
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. 相似文献
18.
Complexation of europium (III) and UO22+ by humic acid was found to be very fast (< 1 m). However, passage through ion exchange resin removed a fraction which decreased as the contact time increased over a 2–3 day period. The dissociation kinetics for UO22+-humate were described by an equation with five first order terms with rate constants ranging from 40.6 m−1 to 5.64×10−3 m−1. The percentage of UO22+ dissociating by the slower paths, comparable to that eluting with the humic acid through the ion exchange resin is assigned to internal site-bound cations (strong binding). The faster dissociating fraction corresponded roughly to the UO22+ removed by the cation exchange resin (weak binding). The time dependence of the weak to strong binding ratio was associated with change in the conformation of the macromolecular humic acid as the cations neutralized the charge repulsions of the anionic humate. 相似文献
19.
To characterize more fully the nature of the fluorophores present in the dissolved organic matter found in seawater, steady state and time-resolved measurements of the luminescence quenching of a number of samples of marine dissolved organic matter with known quenchers, such as iodide, acrylamide and methyl viologen (MV) (1,1′-dimethyl-4,4′-bipyridinium), were compared. Quenching characteristics of these systems were analyzed using Stern-Volmer plots for both intensity and lifetime measurements. The bimolecular quenching constants, κq, for these quenchers were found to decrease in the order MV2+ (κq 1010M−1s−1) > I− (κq 2 × 109 M−1 s−1) >CH2CHCONH2 (κq 2 × 108 M−1 s−1) for the samples measured. The results also show that different samples are quenched to differing extents by the quenchers studied, that ionic strength alters the quenching constants, and that both static and diffusional quenching mechanisms may operate.Such studies are appropriate to the quantification of the reactivity of the singlet states of the chromophores found within marine dissolved organic matter. Although excess energy of the singlet state may be readily transferred to another chemical species, the combination of competing physical deactivation paths and the low concentrations of efficient quenches in the oceans serves to lessen the direct chemical impact of this process. 相似文献