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1.
Cathodic stripping voltammetry (CSV) is used to determine total (after UV-irradiation) and labile dissolved metal concentrations as well as complexing ligand concentrations in samples from the river Scheldt estuary. It was found that even at high added concentrations of catechol (1 m for copper and 0·4 m for iron) and of APDC (1 m for zinc) only part of the dissolved metal was labile (5–58% for copper, 34–69% for zinc, 10–38% for iron); this discrepancy could be explained by the low solubility of iron which is largely present as colloidal material, and by competition for dissolved copper and zinc by organic complexing ligands. Ligand concentrations varied between 28 and 206 n for copper and between 22 and 220 n for zinc; part of the copper complexing ligands could be sub-divided into strong complexing sites with concentrations between 23 and 121 n and weaker sites with concentrations between 44 and 131 n . Values for conditional stability constants varied between (logK′ values) 13·0 and 14·8 for strong and between 11·5 and 12·1 for weaker copper complexing ligands, whereas for zinc the values were between 8·6 and 10·6. The average products of ligand concentrations and conditional stability constants (a-coefficients) were 6 × 102 for zinc and 6 × 106 for copper.The dissolved zinc concentration was found to co-vary with the zinc complexing ligand concentration throughout the estuary. It is argued that the zinc concentration is regulated, in this estuary at least, by interactions with dissolved organic complexing ligands. A similar relationship was apparent between the dissolved copper and the strong copper complexing ligand concentration. The total copper complexing ligand concentrations were much greater than the dissolved copper concentrations, suggesting that only strongly complexed copper is kept in solution.These results provide evidence for the first time that interactions of copper and zinc with dissolved organic complexing ligands determine the geochemical pathway of these metals.  相似文献   

2.
A new method is proposed for the determination of complexing capacities and conditional stability constants for complexes of copper(II) with dissolved organic ligands in seawater. This method is based on ligand competition by the added ligand catechol for free metal ions. The concentration of copper-catechol complex ions is measured with great sensitivity by cathodic stripping voltammetry. The concentration of the free copper ion is calculated from the concentration of copper-catechol complex ions. Ligand concentrations and conditional stability constants are obtained from a titration of the ligands with copper. Two techniques for treatment of the data are compared. A seawater sample, originating from open oceanic conditions, is analysed and two complexing ligands were detected, having concentrations of 1.1 × 10?8 and 3.3 × 10?8 M, and conditional stability constants (log K′CuL) of 12.2 and 10.2, respectively.  相似文献   

3.
Measurements of zinc and zinc complexation by natural organic ligands in the northeastern part of the Atlantic Ocean were made using cathodic stripping voltammetry with ligand competition. Total zinc concentrations ranged from 0.3 nM in surface waters to 2 nM at 2000 m for open-ocean waters, whilst nearer the English coast, zinc concentrations reached 1.5 nM in the upper water column. In open-ocean waters zinc speciation was dominated by complexation to a natural organic ligand with conditional stability constant (log KZnL′) ranging between 10.0 and 10.5 and with ligand concentrations ranging between 0.4 and 2.5 nM. The ligand was found to be uniformly distributed throughout the water column even though zinc concentrations increased with depth. Organic ligand concentrations measured in this study are similar to those published for the North Pacific. However the log KZnL′ values for the North Atlantic are almost and order of magnitude lower than those reported by Bruland [Bruland, K.W., 1989. Complexation of zinc by natural organic-ligands in the central North Pacific. Limnol. Oceanogr., 34, 269–285.] using anodic stripping voltammetry for the North Pacific. Free zinc ion concentrations were low in open-ocean waters (6–20 pM) but are not low enough to limit growth of a typical oceanic species of phytoplankton.  相似文献   

4.
The chemical speciation of iron was determined in the Southern Ocean along a transect from 48 to 70°S at 20°E. Dissolved iron concentrations were low at 0.1–0.6 nM, with average concentrations of 0.25±0.13 nM. Organic iron complexing ligands were found to occur in excess of the dissolved iron concentration at 0.72±0.23 nM (equivalent to an excess of 0.5 nM), with a complex stability of log KFeL′=22.1±0.5 (on the basis of Fe3+ and L′). Ligand concentrations were higher in the upper water column (top 200 m) suggesting in situ production by microorganisms, and less at the surface consistent with photochemical breakdown. Our data are consistent with the presence of stable organic iron-complexing ligands in deep global ocean waters at a background level of ∼0.7 nM. It has been suggested that this might help stabilise iron at levels of ∼0.7 nM in deep ocean waters. However, much lower iron concentrations in the waters of the Southern Ocean suggest that these ligands do not prevent the removal of iron (by scavenging or biological uptake) to well below the concentration of these ligands. Scavenging reactions are probably inhibited by such ligand competition, so it is likely that biological uptake is the chief cause for the further removal of iron to these low levels in waters that suffer from very low iron inputs.  相似文献   

5.
Recent electrochemical measurements have shown that iron (Fe) speciation in seawater is dominated by complexation with strong organic ligands throughout the water column and have provided important thermodynamic information about these compounds. Independent work has shown that iron exists in both soluble and colloidal fractions in the Atlantic Ocean. Here we have combined these approaches in samples collected from a variety of regimes within the Atlantic Ocean. We measured the partitioning of Fe between soluble (< 0.02 μm) and colloidal (0.02 to 0.4 μm) size classes and characterized the concentrations and conditional stability constants of Fe ligands within these size classes. Results suggest that equilibrium partitioning of Fe between soluble and colloidal ligands is partially responsible for the distribution of Fe between soluble and colloidal size classes. However, a significant fraction of the colloidal Fe was inert to ligand exchange as soluble Fe concentrations were generally lower than values predicted by a simple equilibrium partitioning model.In surface waters, strong ligands with conditional stability constants of 1013 relative to total inorganic Fe appeared to dominate speciation in both the soluble and colloidal fractions. In deep waters these ligands were absent, and instead we found ligands with stability constants 12–15 fold smaller that were predominantly in the soluble pool. Nevertheless, significant levels of colloidal Fe were found in these samples, which we inferred must be inert to coordination exchange.  相似文献   

6.
The solubility of iron in oxic waters is so low that iron can be a limiting nutrient for phytoplankton growth in the open ocean. In order to mimic low iron concentrations in algal cultures, Ethylenediaminetetraacetate (EDTA) is commonly used. The presence of EDTA enables culture experiments to be performed at a low free metal concentration, while the total metal concentrations are high. Using EDTA provides for a more reproducible medium. In this study Fe speciation, as defined by EDTA in culture media, is compared with complexation by natural organic complexes in ocean water where Fe is thought to be limited. To grow oceanic species into iron limitation, a concentration of at least 10−4 M EDTA is necessary. Only then does the calculated [Fe3+] concentrations resemble those found in natural sea water, where the speciation is governed by natural dissolved organic ligands at nanomolar concentrations. Moreover, EDTA influences the redox speciation of iron, and thus frustrates research on the preferred source of Fe-uptake, Fe(III) or Fe(II), by algae. Nowadays, one can measure the extent of natural organic complexation in sea water, as well as the dissolved Fe(II) state, and can use ultra clean techniques in order to prevent contamination. Therefore, it is advisable to work with more natural conditions and not use EDTA to create iron limitation. This is especially important when the biological availability of the different chemical fractions of iron are the subject of research. Typically, many oceanic algae in the smallest size classes can still grow at very low ambient Fe and are not easily cultivated into limitation under ambient sea water conditions. However, the important class of large oceanic algae responsible for the major blooms and the large scale cycling of carbon, silicon and other elements, commonly has a high Fe requirement and can be grown into Fe limitation in ambient seawater.  相似文献   

7.
The theory is discussed which describes the distribution of copper ions between a weak ion exchanger, as exemplified by MnO2, and natural organic complexing material in seawater. Application of this theory and experimental procedures are outlined in part II of this series. It is apparent from the theory that titration with Cu2+ of one or more organic complexing ligands can be graphically represented by straight lines; slope and y-axis intercept provide information on the conditional stability constants and the ligand concentrations. Model calculations show that measurement of metal complexation at ligand concentrations higher than normally present in seawater may produce erroneous results because of possible changes in the metal to ligand ratio in the complexes. It is therefore advisable to measure metal complexation in the original, unaltered, water sample.  相似文献   

8.
The distribution of dissolved iron and its chemical speciation (organic complexation and redox speciation) were studied in the northeastern Atlantic Ocean along 23°W between 37 and 42°N at depths between 0 and 2000 m, and in the upper-water column (upper 200 m) at two stations further east at 45°N10°W and 40°N17°W in the early spring of 1998. The iron speciation data are here combined with phytoplankton data to suggest cyanobacteria as a possible source for the iron binding ligands. The organic Fe-binding ligand concentrations were greater than that of dissolved iron by a factor of 1.5–5, thus maintaining iron in solution at levels well above it solubility. The water column distribution of the organic ligand indicates in-situ production of organic ligands by the plankton (consisting mainly of the cyanobacteria Synechococcus sp.) in the euphotic layer and a remineralisation from sinking biogenic particles in deeper waters. Fe(II) concentrations varied from below the detection limit (<0.1 nM) up to 0.55 nM but represented only a minor fraction of 0% to occasionally 35% of the dissolved iron throughout the water column. The water column distribution of the Fe(II) suggests biologically mediated production in the deep waters and photochemical production in the euphotic layer. Although there was no evidence of iron limitation in these waters, the aeolian iron input probably contributed to a shift in the phytoplankton assemblage towards increased Synechococcus growth.  相似文献   

9.
Variations in the speciation of iron in the northern North Sea were investigated in an area covering at least two different water masses and an algal bloom, using a combination of techniques. Catalytic cathodic stripping voltammetry was used to measure the concentrations of reactive iron (FeR) and total iron (FeT) in unfiltered samples, while dissolved iron (FeD) was measured by GFAAS after extraction of filtered sea water. FeR was defined by the amount of iron that complexed with 20 μM 1-nitroso-2-napthol (NN) at pH 6.9. FeT was determined after UV-digestion at pH 2.4. Concentrations of natural organic iron complexing ligands and values for conditional stability constants, were determined in unfiltered samples by titration. Mean concentrations of 1.3 nM for FeR, 10.0 nM for FeT and 1.7 nM for FeD were obtained for the area sampled. FeR concentrations increased towards the south of the area investigated, as a result of the increased influence of continental run off. FeR concentrations were found to be enhanced below the nutricline (below 40 m) as a result of the remineralisation of organic material. Enhanced levels of FeT were observed in some surface samples and in samples collected below 30 m at stations in the south of the area studied, thought to be a result of high concentrations of biogenic particulate material and the resuspended sediments respectively. FeD concentrations varied between values similar to those of FeT in samples from the north of the area to values similar to those of FeR in the south. The bloom was thought to have influenced the distribution of both FeR and FeT, but less evidence was observed for any influence on FeR and FeD. The concentration of organic complexing ligands, which could possibly include a contribution from adsorption sites on particulate material, increased slightly in the bloom area and in North Sea waters. Iron was found to be fully (99.9%) complexed by the organic complexing ligands at a pH of 6.9 and largely complexed (82–96%) at pH 8. The ligands were almost saturated with iron suggesting that the ligand concentration could limit the concentration of iron occurring as dissolved species.  相似文献   

10.
Extractable organic copper using C18 Sep-Pak cartridges was investigated in seawater after laboratory experiment showed that the (C18 Sep-Pak) cartridges were reliable, in open and coastal waters with normal levels of dissolved organic carbon, for the separation of a specific fraction of organo-copper complexes.Given that the Sep-Pak cartridges retain the hydrophobic fraction of the dissolved organic matter, this extraction technique was applied for studying the characteristics of this particular hydrophobic dissolved organic copper fraction (hDOCu) in the north-western Mediterranean waters. Surface distribution of hDOC is influenced by organic matter input from the river Rhone and its estuary as well as the physical processes affecting the primary productivity such as coastal upwelling. By correlating hDOCu concentrations with total dissolved copper and other hydrochemical data such as salinity and dissolved organic carbon, it was possible to examine the behaviour of hDOCu in the water masses of different sources and ages.Marine organic matter has been shown to have high complexing capacity. Productive superficial and intermediate waters as well as deep waters showed relatively high and comparable complexing capacity indicating that old organic matter may have strong complexing sites.  相似文献   

11.
Anodic stripping voltammetry and gel filtration chromatography were used to examine the speciation and organic complexation of copper and lead in seawater. The extent of metal complexation in biologically different water types, the molecular weight ranges of the dissolved organic matter involved in metal-organic associations, and the metal uptake kinetics of these naturally occurring organic species were examined. Analyses of samples from Saanich and Narrows inlets, British Columbia, suggest organic complexation throughout the water column, including anoxic waters of Saanich Inlet. Several fractions of organic material from sedimentary interstitial water in the molecular weight range 500–10,000 were found to complex copper and lead, the concentration of complexing ligands decreasing with depth in the core. Rates of uptake of metals by organic material are slow, of the order of tens of minutes or longer.  相似文献   

12.
To elucidate iron regeneration and organic iron(III)-binding ligand formation during microzooplankton and copepod grazing on phytoplankton, incubation experiments were conducted in the western subarctic Pacific. During 8 days of dark incubation of ambient water and that amended with plankton concentrate, dissolved iron and organic iron(III)-binding ligands accumulated, approximately proportionally to the decrease in chlorophyll a. The observed increases in dissolved iron concentration were much greater than those expected from the consumption of phytoplankton biomass and previously reported Fe:C value of cultured algal cells, suggesting resolution from colloidal or particulate iron adsorbed onto the algal cell surface. When copepods were added to the ambient water, organic iron(III)-binding ligands accumulated more rapidly than in the control receiving no copepod addition, although consumed phytoplankton biomass was comparable between the two treatments. Bioassay experiment using filtrates collected from the incubation experiment showed that organic ligands formed during microzooplankton grazing reduced the iron bioavailability to phytoplankton and suppressed their growth. Moreover, picoplankton Synechococcus sp. and Micromonas pusilla were more suppressed by the organic ligands than the diatom Thalassiosira weissflogii. In conclusion, through microzooplankton and copepod grazing on phytoplankton, organic iron(III)-binding ligands as well as regenerated iron are released into the ambient seawater. Because the ligands lower iron bioavailability to phytoplankton through complexation and the degree of availability reduction varies among phytoplankton species, grazing by zooplankton can shift phytoplankton community structure in iron-limited waters.  相似文献   

13.
The distribution of molecular masses of organic ligands for copper(II) in oceanic water was investigated. The bulk dissolved organic matter (DOM) was fractionated by ultrafiltration and organic ligands were extracted from the resultant fractions by using immobilized metal ion affinity chromatography (IMAC). Contributions of total organic ligands were 2.0–4.4% of the bulk DOM in surface waters, as determined by the UV absorbance. In the distribution of molecular masses of organic ligands, relative contribution of the fraction with low molecular masses (<1000 Da) was dominant (49–62%), while 26–33% of the total organic ligands was in the 1000–10,000 Da fraction, leaving 10–19% in the >10,000 Da fraction. The distribution of molecular masses of organic ligands shifted to higher molecular masses, as compared with that of the bulk DOM. The fluorescence intensities of organic ligands were shown to be associated with carboxyl contents, based on peak excitation/emission wavelengths and the pH-dependence of fluorescence. Two ligand classes with different conditional stability constants (log KCuL′≈7 and 9) were determined from fluorescence quenching of ligand fractions during copper(II) titration. Organic ligands in low molecular mass fractions were relatively weak and strong ligands occurred in higher molecular mass fractions. It is suggested that the weaker ligand sites would consist of two or more carboxyl groups (log KHL′=4), whereas carboxyl groups (log =2), which are protonated at lower pH, and primary amine may additionally contribute to the formation of more stable copper(II) complexes of the stronger ligand.  相似文献   

14.
Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows： Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer （SSL） in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complex- ing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China＇s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.  相似文献   

15.
Shelf break systems are highly dynamic environments. However little is known about the influence that benthic interactions and water mass mixing may have on vertical distributions of iron in these systems. Dissolved Fe (< 0.4 μm) concentrations were measured in samples from nine vertical profiles across the upper slope (150–2950 m water depth) at the Atlantic Ocean–Celtic Sea shelf break. Dissolved iron concentrations varied between less than 0.2 and 5.4 nM, and the resulting detailed section showed evidence of a range of processes influencing the Fe distributions. The near sea floor data were interpreted in terms of release and removal processes. The concentrations of dissolved Fe present in near seabed waters were consistent with release of Fe from in situ remineralisation of particulate organic matter at two upper slope stations, and possibly release from pore water upon resuspension on shelf. Lateral transport of dissolved iron was evident from elevated Fe concentrations in an intermediate nepheloid layer and its advection along isopycnals. Surface waters at the shelf break also showed evidence of vertical mixing of deeper iron-rich waters. These waters contained macronutrients that sustained primary productivity in these otherwise nutrient-depleted surface waters. The data also suggest some degree of stabilisation of relatively high concentrations of iron, presumably through ligand association or as colloids. This study supports the view that lateral export of dissolved iron to the interior of the ocean from shelf and coastal zones and may have important implications for the global budget of oceanic iron.  相似文献   

16.
As part of a larger program focused on understanding the biogeochemistry of large river plumes, we participated in two expeditions during 2000 to sample the Mississippi River plume. Surface water samples were collected using a trace metal clean towed fish and analyzed for total dissolved Fe, organic Fe complexing ligands and their associated conditional stability constants. The ligands in the river plume have conditional stability constants (log K′FeL between 10.5 and 12.3 with an average of 11.2 and standard deviation of 0.6) very similar to ligands found in the open ocean. Comparison of high flow and low flow regimes indicates that variability in flow may be the main cause of the variability in Fe concentrations in the plume. The organic Fe complexing ligands are in greatest excess during a time of higher flow. These ligands are responsible for maintaining very high (5 nM) Fe concentrations throughout the plume. Due to complexation with these organic ligands, the concentration of Fe remains above the Fe-hydroxide solubility level until a salinity above 35 is reached where there appears to be a sink for Fe in the less productive waters. Therefore, Fe is transported a great distance from the river source and is available for biological utilization in the coastal zone.  相似文献   

17.
Copper complexing ligand concentrations in the Daya Bay, Qingdao coast, Jiaozhou Bay, South China Sea and Huanghe Estuary waters were determined by the anodic stripping voltammetry technique. The distribution regularity and the relationship with other parameters were discussed. The results were as follows: Copper complexing ligand concentrations of the South China Sea were a little higher than those of other sea areas, and they were apparently higher than those of the ocean. Compared with the subsurface layer (SSL) in the sea surface microlayer copper complexing ligand concentrations showed an enrichment phenomenon, of which the mechanism is similar to dissolved organic matter. The metal complexing ligand concentration profiles of the South China Sea showed that the value in the sea surface was the highest, then it decreased with depth accruing, and a higher value appeared at the bottom. Copper complexing ligand concentrations were higher than those of cadmium and lead. Ligands in each sea area exhibited a complicated property. In short, the distribution regularity of copper complexing ligand concentrations in China' s coastal waters was consistent with that of other regions in the world. Meanwhile, the positive relationship between the copper complexing ligand concentrations and biological oxygen demand, chemical oxygen demand, dissolved organic carbon, and viscosity were found clearly.  相似文献   

18.
On voyages in the Iceland Basin in 2007 and 2009, we observed low (ca. 0.1 nM) total dissolved iron concentrations [dFe] in surface waters (<150 m), which increased with depth to ca. 0.2–0.9 nM. The surface water [dFe] was low due to low atmospheric Fe inputs combined with biological uptake, with Fe regeneration from microbial degradation of settling biogenic particles supplying dFe at depth. The organic ligand concentrations [LT] in the surface waters ranged between 0.4 and 0.5 nM, with conditional stability constants (log K′FeL) between 22.6 and 22.7. Furthermore, [LT] was in excess of [dFe] throughout the water column, and dFe was therefore largely complexed by organic ligands (>99%). The ratio of [LT]/[dFe] was used to analyse trends in Fe speciation. Enhanced and variable [LT]/[dFe] ratios ranging between 1.6 and 5.8 were observed in surface waters; the ratio decreased with depth to a more constant [LT]/[dFe] ratio in deep waters. In the Iceland Basin and Rockall Trough, enhanced [LT]/[dFe] ratios in surface waters resulted from decreases in [dFe], likely reflecting the conditions of Fe limitation of the phytoplankton community in the surface waters of the Iceland Basin and the high productivity in the Rockall Trough.Below the surface mixed layer, the observed increase in [dFe] resulted in a decrease of the [LT]/[dFe] ratios (1.2–2.6) with depth. This indicated that the Fe binding ligand sites became occupied and even almost saturated at enhanced [dFe] in the deeper waters. Furthermore, our results showed a quasi-steady state in deep waters between dissolved organic Fe ligands and dFe, reflecting a balance between Fe removal by scavenging and Fe supply by remineralisation of biogenic particles with stabilisation through ligands.  相似文献   

19.
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 KZnAPDC′ are calibrated against NTA and EDTA in seawater of several salinities; log KZnAPDC′ 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, KZnL′, 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 KZnL′ 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.  相似文献   

20.
We compute model spectra of the beam attenuation coefficient in surface waters of the Mediterranean Sea. These spectra are used to determine the contribution of the components of seawater (suspended matter, yellow substance, pigments of phytoplankton, and pure water) to the beam attenuation coefficient in different types of seawater. For the surface waters, we establish the relationship between the light scattering coefficient and the attenuation coefficient at a wavelength of 547 nm and determine the background (limiting minimum) value of the coefficient of absorption by the yellow substance in waters of the Mediterranean Sea. It is compared with the values of the same parameter for some other basins (Black Sea, Lake Baikal, Baltic Sea, and oceanic waters).  相似文献   

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