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1.
Results of trace metal analyses performed on two species of Euphausiacea, Meganyctiphanes norvegica and Stylocheiron longicorne, and one species of Decapoda, Sergestes arcticus, collected off the east coast of Corsica, are reported. Analyses were carried out by atomic absorption spectrophotometry and by differential pulse anodic stripping voltammetry.S. arcticus contained lower concentrations of phosphorus (which was also analysed as a biological indicator), cadmium (0.33 μg g−1), copper (17.7 μg g−1), lead (2.13 μg g−1) and zinc (51 μg g−1) than the two Euphausiacea (0.50 μg Cd g−1, 25.4 μg Cu g−1, 4.03 μg Pb g−1 and 59 μg Zn g−1). Moreover, manganese concentrations were low in all the samples.When the results presented here are compared with previous results on phytoplankton and mesozooplankton, there appears to be no trend of trace metal enrichment from phytoplankton to the Decapoda.  相似文献   

2.
The strong species of cadmium(II), copper(II), manganese(II) and nickel(II) in an Antarctic seawater sample are investigated by a method based on the sorption of metal ions on complexing resins. The resins compete with the ligands present in the sample to combine with the metal ions. Two resins with different adsorbing strengths were used. Very stable metal complexes were investigated with the strong sorbent Chelex 100 and weaker species with the less strong resin, Amberlite CG-50. Strong species were detected for three of the considered metal ions, but not for Mn(II). Cu(II) is completely linked to species with a side reaction coefficient as high as log αM(I) = 11.6 at pH = 7.3. The ligand concentration was found to be similar to that of the metal ion, and the conditional stability constant was around 1020 M− 1. In the considered sample, only a fraction of the metal ions Cd(II) and Ni(II) is bound to the strong ligands, with side reaction coefficients equal to log αM(I) = 5.5 and 6.5 at pH = 7.3 for Cd(II) and Ni(II), respectively. These findings were confirmed by the test with the weaker sorbent Amberlite CG-50. It can be calculated from the sorption equilibria that neither Mn(II) nor Ni(II) is adsorbed on Amberlite CG-50 under the considered conditions and, in fact, only a negligible fraction of Mn(II) and Ni(II) was adsorbed. A noticeable fraction of Cd(II) was adsorbed on Amberlite CG-50, meaning that cadmium(II) is partially linked to weak ligands, possibly chloride, while no copper(II) was adsorbed on this resin, confirming that copper(II) is only combined in strong species. These results are similar, but not identical, to those obtained for other seawater samples examined in previous investigations.  相似文献   

3.
Metal-organic complexes were isolated from coastal seawater by adsorption onto octadecyl-bonded silica (SEP-PAK cartridges) and injected into a high-performance liquid chromatograph. Trace metals were identified in the eluate by a four-channel non-dispersive atomic fluorescence detector. Organic complexes of copper, zinc, iron, magnesium, nickel and manganese were found to be present but no complexes of chromium or cadmium were detected. The complexes covered a wide range of polarities with no specific complexes being predominant. Interference from the stainless-steel chromatograph was negligible. The technique provides a minimum estimate of the amount of metal organics and it is suggested that a significant fraction of the metal organics present are too polar to be completely retained by the SEP-PAK cartridges. Typical values of the amounts of trace metal isolated by this technique corresponded to concentrations in the original seawater of >65 ngl?1 (Cu), >27 ngl?1 (Fe) and >41 ngl?1 (Zn).  相似文献   

4.
The organic matter released by the marine phytoplankton species Dunaliella tertiolecta and its physico-chemical interaction with cadmium and copper ions were studied by electrochemical methods (differential pulse anodic stripping voltammetry (DPASV) and a.c. polarography). The interactions with cadmium and copper were studied at the model interface (mercury electrodesolution) and in the bulk phase by measuring the complexing ability of the released organic material.The axenic cultures were grown on different growth media, without and with trace metals and chelators. Culture media were analyzed 10 days after inoculation, containing 5 × 105−1.2 × 106 cells cm−3 when untreated or after separation of cells by gentle centrifugation.It was found that the content and type of the released surface-active material and complexing ligands depend on the initial composition of the growth media. In all cases, strong interaction of excreted organic substances with copper in the bulk phase and with cadmium at the model interface were observed.A rather high value of the complexing capacity, 9.5 × 10−7 mol Cu2+ dm−3, was found in the culture grown on medium without trace metals and chelators (medium I) whereas the surface activity of this culture was not high (0.2 mg dm−3 equivalent to Triton-X-100). Higher contents of surface-active material (0.8 and 1.0 mg dm−3) were found in cultures grown in media with trace metals and without chelators (II and III), accompanied by a high content of complexing ligands (5.8 × 10−7 and 9.5 × 10−7 mol Cu2+ dm−3). However, if the complexing capacity is calculated per cell the values obtained for cultures grown in media II and III (0.79 × 10−15 and 0.98 × 10−15 mol Cu2+ dm−3) are lower than for cultures grown on medium I (1.8 × 10−15 mol Cu2− dm−3). The exceptional adsorption effects and the copper complexing capacity for medium 1, and the presence of cells with degenerative symptoms can be ascribed to stressed growth conditions, and, particularly, to deficiency of metals. A qualitatively similar behaviour has been observed in natural samples of estuarine waters, indicating the existence of stressed conditions during the mixing of fresh and saline waters.  相似文献   

5.
Cadmium is a biologically important trace metal that co-varies with phosphate (PO43− or Dissolved Inorganic Phosphate, DIP) in seawater. However, the exact nature of Cd uptake mechanisms and the relationship with phosphate and other nutrients in global oceans remain elusive. Here, we present a time series study of Cd and PO43− from coastal Antarctic seawater, showing that Cd co-varies with macronutrients during times of high biological activity even under nutrient and trace metal replete conditions. Our data imply that Cd/PO43− in coastal surface Antarctic seawater is higher than open ocean areas. Furthermore, the sinking of some proportion of this high Cd/PO43− water into Antarctic Bottom Water, followed by mixing into Circumpolar Deep Water, impacts Southern Ocean preformed nutrient and trace metal composition. A simple model of endmember water mass mixing with a particle fractionation of Cd/P (αCd–P) determined by the local environment can be used to account for the Cd/PO43− relationship in different parts of the ocean. The high Cd/PO43− of the coastal water is a consequence of two factors: the high input from terrestrial and continental shelf sediments and changes in biological fractionation with respect to P during uptake of Cd in regions of high Fe and Zn. This implies that the Cd/PO43− ratio of the Southern Ocean will vary on glacial–interglacial timescales as the proportion of deep water originating on the continental shelves of the Weddell Sea is reduced during glaciations because the ice shelf is pinned at the edge of the continental shelf. There could also be variations in biological fractionation of Cd/P in the surface waters of the Southern Ocean on these timescales as a result of changes in atmospheric inputs of trace metals. Further variations in the relationship between Cd and PO43− in seawater arise from changes in population structure and community requirements for macro- and micronutrients.  相似文献   

6.
A direct, spectrophotometric method has been adapted for quantitative determination of nitrate concentrations in seawater. The method is based on nitration of resorcinol in acidified seawater, resulting in a color product. The absorption spectrum obtained for the reaction product shows a maximum absorption at 505 nm, with a molar absorptivity of 1.7 × 104 L mol− 1 cm− 1. This method has a detection limit of 0.5 μM and is linear up to 400 μM for nitrate. The advantage of this method is that all reagents are in aqueous solutions without involving cadmium granules as a heterogeneous reactant, as in conventional methods, and therefore is simple to implement. Application of the resorcinol to seawater analysis demonstrated that the results obtained are in good agreement with the conventional approach involving the reduction of nitrate by cadmium followed by diazotization.  相似文献   

7.
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   

8.
The adsorption of Pb2+ and of Cd2+ ions from calcareous Krka river water of various salinities (3, 14, 20 and 38 psu) on calcite (CaCO3, Merck p.a.) was investigated. Simultaneous adsorption of Pb2+ and Cd2+ ions was studied as well. The results suggest that the two ions are adsorbed at different calcite surface sites; Pb2+ remained firmly bound to calcite at all salinities, whereas Cd2+ was firmly bound at low salinities and released at high salinities. Dissolved natural organic ligands at the freshwater-seawater interface (FSI; at 14 psu) promoted and below the FSI (at 20 psu) decreased the adsorption of Cd2+. The experiments were performed at metal concentrations of 8 × 10−8 mol l−1 and at natural pH values around pH 8. Adsorbed amounts of trace metal ions were determined in filtered samples by differential pulse anodic stripping voltammetry (DPASV) with a three-electrode system, after 24 h of equilibration with calcite. Several adsorption models were tested, such as Freundlich's, Langmuir's and Schindler-Stumm's surface coordination model. Adsorption isotherms belong to S-1 class of empirical adsorption isotherms. None gave reasonable values of adsorption constants. The fractional partitioning of adsorbent to the solid phase when normalized to the quantity of adsorbent present (Kd) declined as solid concentration increased. It was found that the surface charge is not responsible for the observed effect. Instead, aggregate size increased, which effected a loss in surface area. This is a reasonable explanation for the observed S-shaped adsorption isotherms curves.  相似文献   

9.
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.  相似文献   

10.
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   

11.
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   

12.
Samples of dead biomass from the marine brown algae Fucus ceranoides, Fucus vesiculosus and Fucus serratus were studied for their ability to remove cadmium from aqueous solutions. The metal sorption process is rapid, with 90% of the metal uptake completed within the first 25 min of contact. The kinetic data was described successfully by a pseudo second order chemical sorption process with rate constants of ca. 0.6 g mmol− 1 min− 1. At pH 4.5, the raw biomass of the three species exhibited equilibrium uptake capacities for Cd as high as 0.8 mmol g− 1 (90 mg g− 1), on a dry weight basis, without chemical pretreatment. These sorption capacities are much higher than those reported for activated carbon and chitin. The sorption of Cd was found to increase as pH increases, reaching a plateau at pH 5.Batch sorption experiments and continuous potentiometric titrations of acid-treated biomass samples in 0.05 M NaNO3 were used to derive thermodynamic binding parameters according to the NICCA model. The total amount of acid sites was 2.4–2.9 mmol g− 1, with median values of the affinity distribution for protons and cadmium ions, log K˜H and log K˜Cd, of 3.7 and 2.69, respectively (conditional values). The apparent heterogeneity of the sorbent was successfully taken into account by the empirical NICCA isotherm, which described very well the competition between protons and metal ions, in contrast with a simpler discrete competitive Langmuir model.The experimental results demonstrate that these seaweeds constitute a promising, efficient, cheap and biodegradable sorbent biomaterial for cadmium removal from wastewaters. This use would represent an example of exploitation of a renewable marine resource in water treatment technologies for the prevention of heavy metal pollution in the environment.  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.
The seawater chemistry of potentially toxic metals can affect their availability to marine organisms. Investigation of the relationship between metal chemistry and metal bioavailability has progressed slowly due to difficulties in controlling and measuring metal speciation in uptake media. Recent work with strong metal chelators such as NTA and EDTA has allowed a closer examination of how metal chemistry relates to biological accumulation and toxicity.1–3 However, the presence of a strong chelator at membrane transport sites and the possible alteration of microenvironments by strong chelators could create unnatural uptake behavior. This study presents another method for stabilizing metal chemistry in accumulation experiments. A cation exchange resin was used to study Mn54 accumulation by a small bivalve Donax variabilus. The resin proved an effective method for buffering manganese chemistry in seawater and could provide a useful tool to look for subtle effects present in other metal buffered seawater systems.  相似文献   

15.
A worldwide literature survey of data on cadmium concentration in the soft tissue of the mussel, Mytilus spp., from 591 stations is presented. These stations are from 13 regions. Geometric means for the regions vary from 0·6 to 3·3 μg g−1 (dry weight) for the Barents Sea and the Northeastern Pacific coast, respectively.The averages of seven of these regions, for which reliable cadmium concentrations in seawater were available, were used to calculate a relationship between cadmium concentrations in seawater and mussel soft tissue. The relationship was highly significant: (Cd) mussel (μg g−1, dry weight) = 0·074 (Cd) water (ng litre−1) + 0·39 (P ≤ 0·0005).This model has been successfully applied in the context of the contamination of the Gironde estuary (France). It can also be used to define a water quality criterion for mussel maturing parks consistent with the quality criterion defined for shellfish for human consumption.  相似文献   

16.
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.
Uptake of the trace metals, Pd, Cd, Hg and Pb, by the marine macroalga, Ulva lactuca, has been studied along a salinity gradient (S = 15–35; pH ~ 8.3) created by batch mixing of synthetic sea water and pure water, both in the absence and presence of humic substances. Factors defining the concentration ratio of metal taken up (w/w) to metal remaining in solution ranged from about 102 mL g− 1 for Cd to 103 mL g− 1 for Pd and Hg. Within experimental error, only the biouptake of Cd appeared to exhibit a dependence on salinity, while the addition of 3 mg L− 1 of humics resulted in a small suppression of Pd and Hg uptake and a moderate enhancement of Pb uptake compared with the humic-free system. Metal internalisation, evaluated from an EDTA wash of the alga, followed the sequence: Hg > Pd > Cd > Pb; and was notably inhibited in the presence of humics for Pb. Metal uptake (as adsorption and internalisation) was modelled using the Windermere Humic Aqueous Model (WHAM, v6) by encoding the macroalga as a polyelectrolytic binding phase whose properties were defaulted to those of aqueous humics in the software database. By setting the “activity” of the binding phase to about 0.1 and systematically reducing the default constants for metal binding, the magnitude of metal uptake by U. lactuca was reproduced. However, for all metals the model predicted a reduction in algal uptake as a function of salinity that was not always observed experimentally. Moreover, calculations performed in the presence of aqueous humic substances and using the earlier fitted constants significantly underestimated metal uptake by U. lactuca. Discrepancies between experimental observations and model calculations, which are attributed to the formation of ternary complexes at the algal surface, suggest that conventional equilibrium speciation considerations alone are not applicable for modelling metal interactions with marine macroalgae.  相似文献   

18.
A complexometric titration technique was employed to measure the total capacity of a variety of marine organisms to adsorb Cu2+. Measured adsorption capacities were 0.22 meq g−1 for phytoplankton, 0.3–1.0 meq g−1 for macrophytes, 1.0–2.5 meq g−1 for zooplankton and 0.3 meq g−1 for suspended particulate matter. The capacity of these materials to adsorb Cu2+ was reduced significantly in the presence of Mg2+ at seawater concentrations. Competition between Mgt2+ and Cu2+ for adsorption sites at pH 6 is described by an average conditional equilibrium constant of 103.7. This constant is such that very little Cu2+ may be adsorbed onto particulates and marine phytoplankton in the presence of Mg2+. Further, primary productivity data and estimates of the detrital carbon sedimentation in Long Island Sound suggest that the flux of particulate carbon is insufficient to remove significant amounts of Cu from the water column to sediments by adsorption mechanisms.  相似文献   

19.
The sublittoral decapod crustacean Pandalus montagui Leach in artificial seawater at 10°C regulates the total body zinc concentration to a constant level in dissolved zinc concentrations up to ca. 22 μg Zn l−1, beyond which there is net accumulation of body zinc. This threshold of zinc regulation breakdown is lower than that in the littoral decapods Palaemon elegans (ca. 93 μg Zn l−1) and Palaemonetes varians (ca. 190 μg Zn l−1) under the same physico-chemical conditions. Correspondingly, zinc uptake rates of the three species of decapods decrease in the order P. montagui > P. elegans > P. varians. It is concluded that regulation of total body zinc concentration is more efficient in decapods adapted to the fluctuating environments of littoral habitats, possibly as a result of changes in permeability of uptake surfaces in combination with improved zinc excretion systems. The moult cycle is important in determining the ability of an individual prawn to regulate zinc. Body zinc in Pandalus montagui consists of at least two pools of zinc exchanging at different rates which the environment. Zinc and copper are not evenly distributed in the tissues of P. montagui.  相似文献   

20.
To clarify the nature of organic metal complexes dissolved in seawater, a ligand exchange reaction between ligands of natural origin and an aminopolycarboxylic acid (EDTA) was used to determine the conditional stability constants of organic metal complexes. The results indicate that more than two organic molecules complexed with copper and zinc exist in surface seawater. It is found that the conditional stability constants of these naturally-occurring organic metal complexes are 1–3 orders of magnitude higher than those of EDTA-Cu and EDTA-Zn complexes. These estimates of the conditional stability constants for the dominant species of organic copper and zinc complexes are 1011.8 and 109.3, respectively, at pH 8.1. The results indicate that these naturally-occurring organic metal complexes are stable species and not easily dissociated or displaced with others in the marine environment.  相似文献   

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