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1.
Catalytic cathodic stripping voltammetry (CSV) preceded by adsorptive collection of complexes of 1-nitroso-2-napthol (NN) can be used to determine iron in seawater. It is shown here that iron(II) is effectively masked in the presence of 2,2-dipyridyl (Dp) so that iron(III) is measured selectively. The concentration of iron(II) is then calculated as the difference between the concentrations of reactive iron (FeR) in the absence and presence of 2 μM Dp, FeR being defined as that which was complexed by 20 μM NN at pH 6.9 in the presence of 1.8 mM H2O2 and 5 ppm sodium dodecyl sulphate. A 30 min reaction time was allowed for Dp to react with iron(II) in seawater prior to the determination of reactive iron(III) using the same conditions as used for FeR. Detection limits of 0.08 nM, 0.077 nM and 0.12 nM were obtained for FeR, iron(III) and iron(II), respectively, using a 60 s deposition time.The method was utilised to determine the redox speciation of iron in the northern North Sea. Concentrations of FeR ranged between 0.8 and 3.5 nM with nutrient-like depth profiles. Iron(II) was found to be present at concentrations up to 1.2 nM, the highest concentrations occurring in the upper 20 m of the water column. 相似文献
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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
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Martha Gledhill Constant M. G. van den Berg Rob F. Nolting Klaas R. Timmermans 《Marine Chemistry》1998,59(3-4)
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
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Klaas R. Timmermans Martha Gledhill Rob F. Nolting Marcel J. W. Veldhuis Hein J. W. de Baar Constant M. G.van den Berg 《Marine Chemistry》1998,61(3-4)
Short-term iron enrichment experiments were carried out with samples collected in areas with different phytoplankton activity in the northern North Sea and northeast Atlantic Ocean in the summer of 1993. The research area was dominated by high numbers of pico-phytoplankton, up to 70,000 ml−1. Maximum chlorophyll a concentrations varied from about 1.0 μg l−1 in a high-reflectance zone (caused by loose coccoliths, remnants from a bloom of Emiliania huxleyi) and about 3.5 μg l−1 in a zone in which the phytoplankton were growing, to about 0.5 μg l−1 in the northeast Atlantic Ocean. From the high-reflectance zone to the northeast Atlantic Ocean, nitrate concentrations increased from 0.5 μM to 6.0 μM. Concentrations of reactive iron in surface water showed an opposite trend and decreased from about 2.6 nM in the high-reflectance zone to <1.0 nM in the northeast Atlantic Ocean. In the research area, no signs of true iron deficiency were found, but iron enrichments in the high-reflectance zone, numerically dominated by Synechococcus sp., resulted in increased nitrate uptake. Ammonium uptake was hardly affected. Strong support for the effect of Fe on cell physiology is given by the increase in the f-ratio. Net growth rates of the phytoplankton (changes in cell numbers over 24 h) were almost unchanged. Phytoplankton collected from the northeast Atlantic Ocean, did not show changes in the nitrogen metabolism upon addition of iron. Net growth rates in these incubations were low or negative, with only slightly higher values with additional iron. 相似文献
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Constant M.G. Van Den Berg 《Marine Chemistry》1984,14(3):201-212
The metal complexing ability of surface water of the Irish Sea has been measured by the MnO2 adsorption method. In all samples strong copper-chelating compounds are present at concentrations of 60–150 nM, with conditional stability constants (log values) of 10.0–10.4. The concentrations of Cu, Pb and Cd in the samples are 16–39 nM, 1–7 nM and 0.1–2 nM, respectively; much less than the ligand concentrations. The organic compounds form complexes with 94–98% of dissolved copper, and therefore constitute the major form of copper in surface water of the Irish Sea. Recalculation of speciation of the inorganic fraction of copper in seawater reveals that the major complex ion is that of CuCO30 (60%), followed by CuOH+ (16%) and Cu(OH)20 (16%). Complexes with borate ions form a small and rather insignificant fraction of 1%. 相似文献
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Evidence for organic complexation of iron in seawater 总被引：1，自引：0，他引：1
Constant M. G. van den Berg 《Marine Chemistry》1995,50(1-4)
Iron occurs at very low concentrations in seawater of oceanic origin and its low abundance is thought to limit primary production in offshore waters (Martin and Fitzwater, 1988). A new electrochemical method, cathodic stripping voltammetry (CSV), is used here to determine the speciation of iron in seawater originating from the Western Mediterranean taking advantage of ligand competition of an added electroactive ligand with the natural organic complexing matter to evaluate whether iron is organically complexed. The measurements indicate that iron occurs 99% (or 99.9% depending on which value is selected for αFe′) complexed by organic complexing ligands throughout the water column of the Western Mediterranean and by analogy probably also in other oceanic waters. The composition of the organic complexing ligands is as yet unknown, but the data indicate a major source from microorganisms (bacteria or phytoplankton) in and immediately below the fluorescence maximum in the upper water column. The organic complexes are apparently reversible releasing iron when the competing ligand is added and binding more iron when its concentration is increased. The organic complexing ligands occur at concentrations well above those of iron ensuring full complexation of this biologically essential element, and buffer the free iron concentration at a very low level against fluctuations as a result of removal by primary producers or inputs from atmospheric sources. The new data indicate that a re-evaluation of the concept of the bioavailable fraction of iron is required. 相似文献
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Jeroen T.M. de Jong Marie Boyé Maria D. Gelado-Caballero Klaas R. Timmermans Marcel J.W. Veldhuis Rob F. Nolting Constant M.G. van den Berg Hein J.W. de Baar 《Marine Chemistry》2007
Dissolved Fe, Mn and Al concentrations (dFe, dMn and dAl hereafter) in surface waters and the water column of the Northeast Atlantic and the European continental shelf are reported. Following an episode of enhanced Saharan dust inputs over the Northeast Atlantic Ocean prior and during the cruise in March 1998, surface concentrations were enhanced up to 4 nmol L− 1 dFe, 3 nmol L− 1 dMn and 40 nmol L− 1 dAl and returned to 0.6 nmol L− 1 dFe, 0.5 nmol L− 1 dMn and 10 nmol L− 1 dAl towards the end of the cruise three weeks later. A simple steady state model (MADCOW, [Measures, C.I., Brown, E.T., 1996. Estimating dust input to the Atlantic Ocean using surface water aluminium concentrations. In: Guerzoni. S. and Chester. R. (Eds.), The impact of desert dust across the Mediterranean, Kluwer Academic Publishers, The Netherlands, pp. 301–311.]) was used which relies on surface ocean dAl as a proxy for atmospheric deposition of mineral dust. We estimated dust input at 1.8 g m− 2 yr− 1 (range 1.0–2.9 g m− 2 yr− 1) and fluxes of dFe, dMn and dAl were inferred. Mixed layer steady state residence times for dissolved metals were estimated at 1.3 yr for dFe (range 0.3–2.9 yr) and 1.9 yr for dMn (range 1.0–3.8 yr). The dFe residence time may have been overestimated and it is shown that 0.2–0.4 yr is probably more realistic. Using vertical dFe versus Apparent Oxygen Utilization (AOU) relationships as well as a biogeochemical two end member mixing model, regenerative Fe:C ratios were estimated respectively to be 20 ± 6 and 22 ± 5 μmol Fe:mol C. Combining the atmospheric flux of dFe to the upper water column with the latter Fe:C ratio, a ‘new iron’ supported primary productivity of only 15% (range 7%–56%) was deduced. This would imply that 85% (range 44–93%) of primary productivity could be supported by regenerated dFe. The open ocean surface data suggest that the continental shelf is probably not a major source of dissolved metals to the surface of the adjacent open ocean. Continental shelf concentrations of dMn, dFe, and to a lesser extent dAl, were well correlated with salinity and express mixing of a fresher continental end member with Atlantic Ocean water flowing onto the shelf. This means probably that diffusive benthic fluxes did not play a major role at the time of the cruise. 相似文献
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Constant Tatchum Noutchogwe Fidèle Koumetio Eliezer Manguelle-Dicoum 《Comptes Rendus Geoscience》2010,342(6):467-474
Structural directions of the southern part of the Adamawa plateau in Cameroon are highlighted by filters applied on the magnetic anomaly map. Determination of the magnitude maxima of (1) the horizontal gradient of the field reduced to the pole, and (2) the analytic signal, allowed a map to be produced showing various lineaments interpreted as the fault system of the studied area. In particular, the faults on the shaded relief map of the horizontal gradient magnitude suggest a slide to the left of the Foumban shear zone in the studied area. Interpretation of the observed anomaly along a profile directed SSE-NNW shows the presence of a magnetized body considered as an intrusion into the granitic basement of probably basaltic volcanic rocks, put in place during the reactivation of the Foumban shear zone. In addition, the observed correlation between the mapped structural directions, the sites of thermo-mineral springs and the hydrographical network shows that the results of this study will be helpful for further hydrogeological research in the studied area. 相似文献
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Conrad S. Chapman Gabriele Capodaglio Clara Turetta Constant M.G. van den Berg 《Marine environmental research》2009,67(1):17-24
Benthic fluxes of copper, copper complexing ligands and thiol compounds in the shallow waters of Venice Lagoon (Italy) were determined using benthic chambers and compared to porewater concentrations to confirm their origin. Benthic copper fluxes were small due to small concentration differences between the porewaters and the overlying water, and the equilibrium concentration was the same at both sites, suggesting that the sediments acted to buffer the copper concentration. Thiol fluxes were ～10 × greater at 50–60 pmol cm?2 h?1, at the two sites. Porewater measurements demonstrated that the sediments were an important source of the thiols to the overlying waters. The overlying waters were found to contain at least two ligands, a strong one, L1 (log K′CuL1 = 14.2) and a weaker one, L2 (log K′CuL2 = 12.5). The concentration of L1 remained relatively constant during the incubation and similar to that of copper, whereas that of L2 was in great excess of copper, its concentration balanced by porewater releases and breakdown, probably due to uptake by microorganisms, similar to that of the thiol compounds. Similarity of the thiol and L2 concentrations and similar complex stability with copper suggest that L2 was dominated by the thiols. The free copper concentration ([Cu´]) in the Lagoon waters was lowered by a factor of 105 as a result of the organic complexation. 相似文献