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1.
Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using 59Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 106M−1s−1 and 20 M−1s−1, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)3o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands. 相似文献
2.
The hydrolysis of silicic acid, Si(OH)4, was studied in a simplified seawater medium (0.6 M Na(Cl)) at 25°C. The measurements were performed as potentiometric titrations (hydrogen electrode) in which OH− was generated coulometrically. The total concentration of Si(OH)4, B, and log[H+] were varied within the limits 0.00075 B 0.008 M and 2.5 -log[H+] 11.7, respectively. Within these ranges the formation of SiO(OH)3− and SiO2(OH)22− with formation constants log β−11(Si(OH)4 SiO(OH)3− + H+) = −9.472 ±0.002 and log β−21(Si(OH)4 SiO2(OH)22− + 2H+) = −22.07 ± 0.01 was established. With B > 0.003 M polysilicate complexes are formed, however, with -log[H+] 10.7 their formation does not significantly affect the evaluated formation constants. Data were analyzed with the least squares computer program LETAGROPVRID. 相似文献
3.
Calibration of a chalcogenide glass membrane, Fe(III)ISE [Fe2.5(Ge28Sb12Se60)97.5], in buffered saline media has been undertaken in order to assess the suitability of this ISE for seawater analyses. The electrode slopes in saline citrate and salicylate buffers were 26.3 and 28.2 mV/decade, respectively, for Fe3+ concentrations ranging from 10−10 M to less than 10−25 M Fe3+. The calibration lines in the citrate and salicylate buffers were essentially collinear with the response in unbuffered chloride-free standards containing >10−5 M Fe3+, demonstrating that the response of the FeISE is unaffected by chloride ions. A mechanism involving a combination of charge transfer and ion-exchange of Fe(III), at the electrode diffusion layer, can be used to explain the ≈30 mV/decade slope of the FeISE. The response of the FeISE in UV photooxidised seawater containing 8 nM total Fe was measured as the pH was changed from 8.27 to 3.51. The slope of the response was 24.2 mV/decade [Fe3+] calculated as a function of pH using Fe(III) hydrolysis constants for seawater. Moreover, the response was essentially collinear with that in citrate buffers and in unbuffered solutions containing >10−5 M Fe3+ and the slope for the combined data was 26.2 mV/decade. This study was restricted to organic-free seawater because the certainty in Fe(III)–ligand stability constants is insufficient to warrant the selection of an ideal calibration buffer system, and there is evidence that powerful chelating ligands (e.g., EDTA along with humic and fulvic acids) may alter the response of the Fe(III)ISE. The Fe dissolution rate of the FeISE in UV photooxidised seawater was found to be 1.6×10−2 nmol Fe/min, as measured by cathodic stripping voltammetry (CSV). This would contaminate a 100-ml sample by 0.8–1.6 nM Fe over a typical measurement period of 5–10 min obtained using a stability criterion of 0.5 mV/min. Various methods are proposed for reducing the level of contamination in open ocean samples that contain sub-nanomolar concentrations of iron. The FeISE has the potential to detect free Fe3+ at concentrations typically found in natural seawater. 相似文献
4.
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
5.
The northern part of Okinawa Island suffers from red soil pollution—runoff of red soil into coastal seawater—which damages coastal ecosystems and scenery. To elucidate the impacts of red soil pollution on the oxidizing power of seawater, hydrogen peroxide (HOOH) and iron species including Fe(II) and total iron (Fe(tot), defined as the sum of Fe(II) and Fe(III)) were measured simultaneously in seawater from Taira Bay (red-soil-polluted sea) and Sesoko Island (unpolluted sea), off the northern part of Okinawa Island, Japan. We performed simultaneous measurements of HOOH and Fe(II) because the reaction between HOOH and Fe(II) forms hydroxyl radical (•OH), the most potent environmental oxidant. Gas-phase HOOH concentrations were also measured to better understand the sources of HOOH in seawater. Both HOOH and Fe(II) in seawater showed a clear diurnal variation, i.e. higher in the daytime and lower at night, while Fe(tot) concentrations were relatively constant throughout the sampling period. Fe(II) and Fe(tot) concentrations were approximately 58% and 19% higher in red-soil-polluted seawater than in unpolluted seawater. Gas-phase HOOH and seawater HOOH concentrations were comparable at both sampling sites, ranging from 1.4 to 5.4 ppbv in air and 30 to 160 nM in seawater. Since Fe(II) concentrations were higher in red-soil-polluted seawater while concentrations of HOOH were similar, •OH would form faster in red-soil-polluted seawater than in unpolluted seawater. Since the major scavenger of •OH, Br−, is expected to have similar concentrations at both sites, red-soil-polluted seawater is expected to have higher steady-state •OH concentrations. 相似文献
6.
Virender K. Sharma Aurelie Moulin Frank J. Millero Concetta De Stefano 《Marine Chemistry》2006,99(1-4):52
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− anionsThe stability constants have been fitted toafter 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. 相似文献
Mg2+ + Cys2− = MgCys
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.
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
9.
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
10.
S. E. Ingle 《Marine Chemistry》1975,3(4):301-319
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. 相似文献
11.
The rates of the reduction of Cr(VI) with S(IV) were measured in deaerated NaCl solution as a function of pH, temperature and ionic strength. The rates of the reaction were found to be first order with respect to Cr(VI) and second order with respect to S(IV), in agreement with previous results obtained at concentrations two order higher than the present study. The reaction also showed a first-order dependence of the rates on the concentration of the proton and a small influence of temperature with an apparent energy of activation ΔHapp of 22.8 ± 3.4 kJ/mol. The rates were independent of ionic strength from 0.01 to 1 M. The rate of Cr(VI) reduction is described by the general expression
−d[Cr(VI)]/dt=k[Cr(VI)][S(IV)]2