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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   

2.
Evidence for organic complexation of iron in seawater   总被引：1，自引：0，他引：1  
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   

3.
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   

4.
A sensitive method for iron determination in seawater has been adapted on a submersible chemical analyser for in situ measurements. The technique is based on flow injection analysis (FIA) coupled with spectrophotometric detection. When direct injection of seawater was used, the detection limit was 1.6 nM, and the precision 7%, for a triplicate injection of a 4 nM standard. At low iron concentrations, on line preconcentration using a column filled with 8-hydroxyquinoline (8HQ) resin was used. The detection limit was 0.15 nM (time of preconcentration = 240 s), and the precision 6%, for a triplicate determination of a 1 nM standard, allowing the determination of Fe in most of the oceanic regimes, except the most depleted surface waters. The effect of temperature, pressure, salinity, copper, manganese, and iron speciation on the response of the analyser was investigated. The slope of the calibration curves followed a linear relation as a function of pressure (Cp = 2.8 × 10− 5P + 3.4 × 10− 2 s nmol− 1, R2 = 0.997, for Θ = 13 °C) and an exponential relation as a function of temperature (CΘ = 0.009e0.103Θ, R2 = 0.832, for P = 3 bar). No statistical difference at 95% confidence level was observed for samples of different salinities (S = 0, 20, 35). Only very high concentration of copper (1000 × [Fe]) produced a detectable interference. The chemical analyser was deployed in the coastal environment of the Bay of Brest to investigate the effect of iron speciation on the response of the analyser. Direct injection was used and seawater samples were acidified on line for 80 s. Dissolved iron (DFe, filtered seawater (0.4 μm), acidified and stored at pH 1.8) corresponded to 29 ± 4% of Fea (unfiltered seawater, acidified in line at pH 1.8 for 80 s). Most of Fea (71 ± 4%) was probably a fraction of total dissolvable iron (TDFe, unfiltered seawater, acidified and stored at pH 1.8).  相似文献   

5.
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   

6.
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   

7.
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   

8.
《Marine Chemistry》2007,103(1-2):61-75
The capacity of natural dissolved organic matter (DOM) produced during the onset, development and decay of a simulated bloom of the marine diatom Skeletonema costatum to complex free copper has been followed for a 2 week period. Copper binding capacity of the culture was measured by anodic stripping voltammetry (ASV) with a hanging mercury drop electrode (HMDE). The concentration of dissolved organic carbon (DOC) and two fluorophores, M (humic-like, Ex/Em: 320 nm/410 nm) and T (protein-like, Ex/Em: 280 nm/350 nm), were followed during the course of the incubation. Models using DOC concentrations alone could not accurately predict the complexing capacity of the culture, especially at the end of the bloom, and better predictions were obtained when fluorescence measurements were considered. They were helpful in characterising two types of copper ligands produced in the culture. The first type, traced by the fluorescence of peak T, was related to labile DOC directly exuded by phytoplankton. The second type, traced by the fluorescence of peak M, was the refractory humic-like material presumably produced in situ as a by-product of the bacterial degradation of phytogenic materials. During the onset and development of the bloom (days 0 to 7), the fluorescence of peak T explains 60–80% of the total complexing capacity of the culture, suggesting that exuded “protein-like” compounds among other exuded complexing agents efficiently complexed free copper. On the contrary, during the decay (days 8 to 13), these ligands were replaced by humic substances as the complexing agent for copper.  相似文献   

9.
We report dissolved iron (Fed) concentrations measured in the upper 600 m in the central region of the Gulf of California (GC) under spring conditions. Our results showed the complex nature of Fe cycling within the GC. In the northern region of the study area, surface waters were relatively enriched, with Fed concentrations >5.0 nM, which can be partially explained by an atmospheric source. These concentrations are 12 times higher than those found in the adjacent Pacific Ocean. In contrast, Fed depth profiles in the southern region did not show any Fed surface enrichment (concentrations <1.5 nM) because of particle scavenging and higher stratification of the water-column. The most southern station in our area of study was the most stratified and showed an excess Fed and PO4 with respect to NO3, conditions favorable for nitrogen fixation. This station also showed the least negative surface value of N* of all stations. However, despite the adequate levels of Fed and PO4 at that location, the surface temperature (22.6 °C) was probably not high enough for diazotrophs to develop. A slight increase in Fed levels in intermediate waters at the southern region was associated with the oxygen minimum zone. Finally, our results suggest that remineralization of organic matter is probably the major source of Fed in subsurface waters of the GC.  相似文献   

10.
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   

11.
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   

12.
In the Eastern North Atlantic Ocean iron (Fe) speciation was investigated in three size fractions: the dissolvable from unfiltered samples, the dissolved fraction (<0.2 μm) and the fraction smaller than 1000 kDa (<1000 kDa). Fe concentrations were measured by flow injection analysis and the organic Fe complexation by voltammetry. In the research area the water column consisted of North Atlantic Central Water (NACW), below which Mediterranean Overflow Water (MOW) was found with the core between 800 and 1000 m depth. Below 2000 m depth the North Atlantic Deep Water (NADW) proper was recognised. Dissolved Fe and Fe in the <1000 kDa fraction showed a nutrient like profile, depleted at the surface, increasing until 500–1000 m depth below which the concentration remained constant. Fe in unfiltered samples clearly showed the MOW with high concentrations (4 nM) compared to the overlying NACW and the underlying NADW, with 0.9 nM and 2 nM Fe, respectively. By using excess ligand (Excess L) concentrations as parameter we show a potential to bind Fe. The surface mixed layer had the highest excess ligand concentrations in all size fractions due to phytoplankton uptake and possible ligand production. The ratio of Excess L over Fe proved to be a complementary tool in revealing the relative saturation state of the ligands with Fe. In the whole water column, the organic ligands in the larger colloidal fraction (between 0.2 μm and 1000 kDa) were saturated with Fe, whereas those in the smallest fraction (<1000 kDa) were not saturated with Fe, confirming that this fraction was the most reactive one and regulates dissolution and colloid aggregation and scavenging processes. This regulation was remarkably stable with depth since the alpha factor (product of Excess L and K′), expressing the reactivity of the ligands, did not vary and was 1013. Whereas, in the NACW and the MOW, the ligands in the particulate (>0.2 μm) fraction were unsaturated with Fe with respect to the dissolved fraction, thus these waters had a scavenging potential.  相似文献   

13.
The influence of organic ligands on natural phytoplankton growth was investigated in high-nitrate low-chlorophyll (HNLC) waters and during a phytoplankton bloom induced by a mesoscale iron enrichment experiment (SEEDS II) in the western subarctic Pacific. The growth responses of the phytoplankton in the treatments with iron complexed with model ligand were compared with those with inorganic iron or a control. Desferrioxamine B and protoporphyrin IX were used as models for hydroxamate-type siderophore and tetrapyrrole-type cell breakdown ligand, respectively. In the HNLC water, iron associated with protoporphyrin IX especially stimulated smaller phytoplankton (<10 μm) growth, 1.5-fold more than did inorganic iron. Surprisingly, only the addition of protoporphyrin IX stimulated small phytoplankton growth, suggesting that these cell breakdown ligands might be more bioavailable for them. The protoporphyrin IX’s stimulatory effect on small phytoplankton was not observed during bloom decline phase. The growth of phytoplankton was inhibited in the treatment with desferrioxamine B-complexed iron, suggesting its low bioavailability for the natural phytoplankton community. Its inhibitory effects were particularly pronounced in pico-eukaryotic phytoplankton. During the iron-induced bloom, the phytoplankton’s iron-stress response gradually increased with the desferrioxamine B concentration, suggesting that the competition for iron complexation between natural ligands and desferrioxamine B affected phytoplankton growth. However, the pico-eukaryotes did seem better able to utilize the desferrioxamine B-complexed iron during the bloom-developing phase. These results indicate that the iron bioavailability for phytoplankton differs between bloom-developing and bloom-decline phases.  相似文献   

14.
The chemical speciation of Cu and Zn was investigated by voltammetric titration methods in the surface waters (10 m) of the western Black Sea during an Istanbul–Sevastopol cruise conducted in November 1998. Supporting parameters (temperature (T), salinity (S), pH, alkalinity (Alk), suspended particulate matter (SPM) and dissolved and particulate 234Th) were obtained in order to distinguish hydrographic features against involvement of the metals in biogeochemical processes. In the Turkish continental slope region, the cruise track intersected a narrow vein of colder water originating on the western shelf. The core of this cold water vein was characterised by a relatively low salinity, higher specific alkalinity and higher metal (especially Cu) and metal-binding ligand concentrations.A very large portion of Cu (93–99.8%) and Zn (82–97%) was organically complexed. The degree of complexation was highest in shelf waters and lowest in the central gyre. Titration data for Cu were modelled by two classes of organic binding ligands characterised by (CL1=3–12 nM, log K1′=13.1–13.9) and (CL2=20–70 nM, log K2′=9.4–11.2). These ligands occurred mainly in the ‘dissolved’ phase, as defined by 0.4-μm filtration. The stronger Cu-binding ligand seemed to be produced in situ in response to Cu concentration, whereas the weaker Cu-binding ligand appeared to be derived from terrestrial sources and/or reducing shelf sediments. Titration results for Zn were generally represented by one class of ligands (CL1=8–23 nM, log K1′=9.4–10.2), which were almost uniformly distributed between the ‘dissolved’ (78±8%) and the particulate phase (22±8%). The concentration of these strong Zn-binding ligands showed a very good correlation with SPM (r2=0.64), which improved when the dissolved ligands alone were considered (r2=0.78). It is hypothesised that these ligands were produced in situ by the bacterial breakdown of particulate organic matter.  相似文献   

15.
The chemical speciation of dissolved mercury in surface waters of Galveston Bay was determined using the concentrations of mercury-complexing ligands and conditional stability constants of mercury-ligand complexes. Two classes of natural ligands associated with dissolved organic matter were determined by a competitive ligand exchange-solvent solvent extraction (CLE-SSE) method: a strong class (Ls), ranging from 19 to 93 pM with an average conditional stability constant (KHgLs) of 1028, and a weak class (Lw) ranging from 1.4 to 9.8 nM with an average KHgLs of 1023. The range of conditional stability constants between mercury and natural ligands suggested that sulfides and thiolates are important binding sites for dissolved mercury in estuarine waters. A positive correlation between the estuarine distribution of dissolved glutathione and that of mercury-complexing ligands supported this suggestion. Thermodynamic equilibrium modeling using stability constants for HgL, HgClx, Hg(OH)x, and HgCl(OH) and concentrations of each ligand demonstrated that almost all of the dissolved mercury (> 99%) in Galveston Bay was complexed by natural ligands associated with dissolved organic matter. The importance of low concentrations of high-affinity ligands that may originate in the biological system (i.e., glutathione and phytochelatin) suggests that the greater portion of bulk dissolved organic matter may not be important for mercury complexation in estuarine surface waters.  相似文献   

16.
The speciation of lead at a site in the South San Francisco Bay was determined using a combination of physical size fractionation and electrochemical analyses. The ‘ total dissolvable ’ Pb was 8·1 nM from analysis of an acidified unfiltered sample. The ‘ dissolved ’ Pb was equal to 0·20 nM (41 ng l−1), only 2·5% of the ‘ total dissolvable ’ Pb. The difference yielded the ‘ particulate ’ Pb equal to 7·9 nM (1·6 μg l−1). Results from crossflow ultrafiltration indicated that almost all (0·19 nM) of the dissolved Pb was ‘ in solution ’ [<10K nominal molecular weight (MW)] and that colloidal Pb (10K MW to 0·2 μm)accounted for onlyc. 1% of the dissolved Pb at this station. This small concentration (0·01 nM) of colloidal Pb may be attributed to the low amount of organic carbon associated with colloid size fraction as determined by dissolved organic carbon analyses.The chemical speciation of lead was determined in the dissolved sample and ultrafiltered sub-sample. Differential pulse anodic stripping voltammetry (DPASV) on a thin mercury film (TMF) rotating glassy carbon disk electrode (RGCDE) was used to distinguish the kinetically labile inorganic species (Pb′) from the Pb-chelated by organic ligands (PbLi). Lead titration results were similar for both samples revealing that Pb′, PbLiand excess unbound ligands were present primarily in the ultrafiltrate, rather than in the colloidal phase. The titration data can be interpreted as dissolved Pb being influenced by two classes of Pb-binding ligands. In the dissolved sample, the concentration of the stronger class of ligands was [L1]=0·89±0·35 nM, with a conditional stability constant ofKcondL1,Pb′=3±1×1010M−1. The weaker class was [L2]=12·8±1·9 nM, withKcondL1,Pb′=4±1×108 M−1. The presence of these ligands, in excess of the dissolved Pb, resulted in [Pb′]=7±2 pM and [Pb2+]=0·3 pM (62 pg l−1). While less than 2·4% of the ambient Pb was ‘ in solution ’, it existed chiefly in the form of organic complexes with [PbL1]=0·15 nM and [PbL2]=0·03 nM. More significantly, there were large concentrations of unchelated Pb-binding ligands, (Li′), available to buffer the free Pb2+concentration in the event of perturbations in dissolved Pb.  相似文献   

17.
-By the electroanalysis method combining the complexation titrating technique with the investigation of ip-Ea* characteristic curves, this paper measures apparent complexing capacities of trace heavy-metals in water samples from the Huanghe River Estuary. The results show that the order of apparent complexing capacities of trace heavy-metals in the samples isCu>Cd>Pb,and that apparent complexing capacities of near shore sample are higher than those far from shore. The effect of ultraviolet irradiation on the dissociation of organic ligands and the adsorption effect of cell walls (cells being treated with acid and seawater respectively) are investigated. The reduction (on electrodes) mechanism of species of trace heavy-metals in seawater is approached by ip-Ea* characteristic curves.  相似文献   

18.
The ubiquitous algal species, Emiliania huxleyi, was incubated in sea water supplemented only with nitrate and phosphate (N and P) without chelating agents to control metal speciation. Growth was slow in a “low-iron” culture containing 1.3 nM iron and was found to be iron-limited, growth-accelerating when a 1-nM iron addition was made. The growth rate in a “high-iron” culture (5.4 nM iron) was greater, reaching 0.4 div day−1 but this culture too was found to have become iron-limited when a 9-nM iron addition was made on day 17 of the incubation. Both cultures were found to release iron-complexing ligands in excess of the iron concentration, 6 nM in the low-iron culture, and 10 nM in the high-iron culture. More ligands were produced after the iron addition taking the ligand concentration to 11 nM in the low-iron culture. The data show that the ligands are released in response to the iron addition, when at least some of the iron had already been taken up. This type of release is contrary to the concept of a siderophore, which is supposed to be released in periods of lack of iron; however the increase in the ligand concentration is similar to that released by the natural community in response to the iron addition in the IRON-EX II experiment [Rue, E.L., Bruland, K.W., 1997. The role of organic complexation on ambient iron chemistry in the equatorial Pacific Ocean and the response of a mesoscale iron addition experiment. Limnol. Oceanogr. 42, 901–910]. The enhanced growth in the cultures when more iron was added indicated that the organically complexed iron present in the cultures was not immediately available to the organisms (or at least not at sufficiently high rate), and that the organisms responded to freshly added, inorganic, iron.  相似文献   

19.
Two independent voltammetric techniques, differential pulse cathodic stripping voltammetry (DPCSV) and differential pulse anodic stripping voltammetry (DPASV), determined that 95% of the dissolved zinc is organically complexed at two depths (60 and 150 m) within the surface euphotic zone at an open ocean station in the Northeast Pacific. Average values for the concentrations of the natural zinc-complexing organic ligands (CL) obtained from duplicate determinations at these two depths by DPCSV versus DPASV are in excellent agreement: 1.60 ± 0.01 versus 1.76 ± 0.03 nM at 60 m, and 2.14 (n=1) versus 2.22 ± 0.06 nM at 150 m. Average values for the conditional stability constants (with respect to free Zn2+) of the natural zinc-organic complexes (log K′ZnL) from duplicate determinations at both depths by DPCSV versus DPASV are 10.3 ± 0.2 versus 11.2 ± 0.2. Additional research is required to assess the significance of the difference in the conditional stability constants determined by these two techniques. These results confirm recent observations that strong zinc complexes formed with an organic ligand class existing at nanomolar concentrations dominates zinc speciation in the North Pacific.  相似文献   

20.
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   

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