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1.
Iron coordination and redox reactions in synthetic and coastal seawater were investigated at nanomolar concentrations using 59Fe radiometry and ion-pair solvent extraction of iron chelated by sulfoxine (8-hydroxyquinoline-5-sulfonate) and BPDS (bathophenanthroline disulfonate). Using sulfoxine, we determined the rate at which the monomeric Fe(III) hydroxide species present in seawater of pH 8 are complexed by the microbial siderophore deferriferrioxamine B and the synthetic chelator EDTA (ethylenediaminetetraacetic acid). Forward rate constants of 2 × 106M−1s−1 and 20 M−1s−1, respectively, were obtained. The kinetics of these reactions have not been measured previously at pH values near that of seawater. Conditional equilibrium constants measured for the Fe(III)-EDTA system are consistent with published stability constants for EDTA complexes and for Fe(III) hydrolytic equilibria minus the neutral Fe(OH)3o species, suggesting it is not quantitatively significant near pH 8. Commercial humic acid was found to have sufficient affinity for iron to compete with Fe(III) hydrolysis in seawater, and limited evidence was obtained for an interaction with dissolved organic matter in coastal seawater.In our investigations of redox reactions using BPDS to trap Fe(II) produced in the medium, we observed enhanced photoreduction of Fe(III) by humic acid as well as reduction induced by solutes released from phytoplankton in seawater of pH 8. Although the method is sensitive enough to work at near-oceanic levels of iron, the difficulty in distinguishing Fe(II) generated by Fe(III)-BPDS interactions from Fe(II) produced by other means limits its utility. This analytical ambiguity may be generalizable to other methods which measure ferrous iron in seawater using Fe(II)-specific ligands. 相似文献
2.
3.
Jeffrey B. Frithsen 《Estuarine, Coastal and Shelf Science》1984,19(5):523-539
A radionuclide addition experiment was conducted in a large-scale experimental mesocosm to study the behaviour and fate of trace metals in a coastal marine environment. Twelve radionuclides (7Be, 109Cd, 134Cs, 58Co, 60Co, 51Cr, 59Fe, 54Mn, 203Hg, 233Pa, 113Sn, and 65Zn) were added and their concentrations in benthic organisms and sediments were measured during the following nine months. The ability of benthic organisms to concentrate radionuclides was related to the vertical distribution and feeding behaviour of the organisms. Surface living fauna incorporated more radionuclides than deeper fauna. Calculations of total annual radionuclide incorporation by benthic fauna indicated that meiofauna incorporated a similar amount of the labelled metals as the macrofauna, even though the latter have a larger standing stock biomass. These calculations suggest that benthic metazoan fauna can annually cycle from 1% (Sn) to nearly 50% (Cd) of the amount of added radionuclides measured in sediments. 相似文献
4.
William G. Sunda 《Marine Chemistry》1984,14(4):365-378
Equilibria between Chelex 100* and manganese, zinc and cadmium ions were used to determine the complexation of these trace metals in 36‰ Gulf Stream seawater at 25°C and pH 8.2. The method utilized radiotracers (54Mn, 65Zn, and 109Cd) to quantify trace metal adsorption from trace metal-amended seawater and from seawater containing a series of ethylenediaminetetracetate (EDTA)—metal ion buffers. Results were consistent with Chelex adsorption of both trace metal ions and trace metal—EDTA chelates. Equilibrium models fitted to the data were used to establish conditional stability constants for Chelex adsorption of manganese, zinc and cadmium ions and for adsorption of EDTA-chelates. These models also yielded ratios of free metal ions to total dissolved trace metal concentrations in seawater: 10−0.1 for manganese, 10−0.2 for zinc, and 10−1.5 for cadmium. Independent measurements with a cadmium ion-selective electrode also yielded a free: total cadmium ratio of 10−1.5. 相似文献
5.
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
6.
A.I. Lillebø M. Válega M. Otero M.A. Pardal E. Pereira A.C. Duarte 《Estuarine, Coastal and Shelf Science》2010
It has been shown that salt marshes may function as efficient sinks for contaminants, namely for mercury. At the rhizo-sediment Hg may be associated with Mn and Fe oxyhydroxides, precipitated as sulphides or incorporated into organic matter. However, to our knowledge, in situ studies have not focused on the related processes at a daily or tidal cycle scales. Thus, the present work aims to study the effect of a common salt marsh halophyte in temperate latitudes (Sarcocornia perennis) on dissolved Fe, Mn and Hg concentrations in the water column. The in situ approach was carried out at a mercury-contaminated salt marsh and at the adjacent non-vegetated area (distance ≤ 4 m), covering two consecutive tidal cycles in order to include the photosynthetic active period and the night processes. During high tide no daily or spatial effects were observed on the concentrations of Mn, Fe and Hg in the water column, due to the dilution effect of the incoming seawater. During low tide the concentrations of Mn, Fe and Hg were significantly higher in the overlaying water column of the salt marsh. At S. perennis mats the concentration of dissolved total Hg was significantly related with the concentration of Mn (r = 0.459, p = 0.028, n = 23), but not with that of Fe (r = 0.367, p = 0.085, n = 23) while no significant relations were found at the adjacent non-vegetated sediments. 相似文献
7.
The protonization constant of HS? (K12) has been determined potentiometrically (glass electrode) at atmospheric pressure in synthetic seawater in the salinity range 2.5–40‰ at 5 and 25°C and in NaCl solutions in the formal ionic strength of 0.1–0.8 M at 5 and 25°C. The difference between synthetic seawater and an NaCl solution with the same formal ionic strength can be explained in terms of the complexation of H+ by sulphate in seawater. These results can be used to compare the pH scales suggested by Hansson (1973c) and Bates (1975). Furthermore, comparison between the present values of K12 and those of Goldhaber and Kaplan (1975) makes it possible to compare the conventional pH scale with Hansson's titration pH scale. The conditional protonization constant of HS? in seawater of different salinities can be used to modify the Gran plots (Hansson and Jagner, 1973) for alkalinity measurements in anoxic seawater. Ion-pair formation between HS? and Mg2+ or Ca2+ seems to be very weak. 相似文献
8.
The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd and Pb in seawater was investigated in the Chukchi and Beaufort Seas of the western Arctic Ocean in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable metal (TDM) and dissolved metal (DM), respectively. The concentration of labile particulate metal (LPM) was estimated with the difference between that of TDM and DM. The concentrations of TDAl, TDMn, TDFe, TDCo and TDPb varied substantially in the study area. The high concentrations occurred at stations near the Bering Strait, in the Mackenzie delta, and above reductive sediments on the shelf and slope. These elements were mostly dominated by labile particulate species, such as Fe?CMn oxides and species adsorbed on terrestrial clay. DCo was correlated with DMn over the study area (r?=?0.78, n?=?135), and the slope of the regression line was 27 times higher at a pelagic station than at a shelf station. TDNi, TDCu, TDZn and TDCd showed relatively small variations and were generally dominated by dissolved species. There was a moderate correlation between DCd and phosphate for all samples (r?=?0.79), whereas there were no significant correlation between the other DMs and nutrients. TDNi and TDCu showed a remarkable linearity for most stations except those near the Bering Strait (R 2?=?0.95, n?=?126). These results suggest that biogeochemical cycling including uptake by phytoplankton and remineralization from settling particles has only minor control over the distribution of trace metals in this area. Using the present data, the annual input of bioactive trace metals form the Bering Strait and the Mackenzie River was estimated. Also, the trace metal compositions of major water masses were evaluated. The dissolved elemental ratio was P:Al:Mn:Fe:Co:Ni:Cu:Zn:Cd?=?1:1.2?×?10?2:4.4?×?10?4:1.4?×?10?3:3.7?×?10?5:3.7?×?10?3:1.4?×?10?3:4.5?×?10?3:2.2?×?10?4 for Canada Basin deep water (CBDW). This ratio was significantly different from that for Pacific deep water and Bering Sea water, suggesting substantial modification of the trace metal compositions of seawater in the study area. 相似文献
9.
The activity of NaCl in artificial seawater was measured potentiometrically with Na+- and Cl? -sensitive electrodes. The salinity of the solutions, examined at 25°C, ranged from 10–40‰ salinity. The change in the activity from 5–25°C was measured at 35‰ salinity.The molal mean activity coefficient of NaCl in 35‰ seawater at 25°C is 0.667. The relative partial molal enthalpy of NaCl in 35‰ seawater is ?130 ±50 cal mol?1. This value is in good agreement with the value measured in pure 0.72 M NaCl.The results were compared with activity coefficients predicted by a specific interaction model and by an ion association model. Good agreement was found in both cases. 相似文献
10.
A total of 150 samples were collected at a 10-days' anchor station in the Bornholm basin (55° 31.1′N, 15° 32.1′E) and analyzed for dissolved (< 0.4 μm) and particulate trace metals. For dissolved Mn, large gradients have been found in the vertical distribution with minimum concentrations (< 0.2 μgl?1) in the halocline zone and considerably higher values in the deep waters (up to 50 μgl?1). Ultrafiltration studies indicate that dissolved Mn is probably present as Mn2+ in the oxygenated bottom layer. The primary production process was not evident in the particulate Mn profile; the suspended particulate material (SPM), however, shows a considerable enrichment with depth, apparently due to Mn-oxide precipitation.The distribution of dissolved Fe was rather homogeneous, with average concentrations throughout the water column between 0.86 and 1.1 μgl?1, indicating that the oxidation of Fe2+ ions released from the sediments must already be complete in the very near oxidation boundary layer. Relatively high concentrations of particulate Fe were actually measured in the bottom layer, with the maximum mean of 11.2 μgl?1 at 72 m. Similarly to Mn, the profile of particulate Fe does not reflect the SPM curve of the eutrophic layer. On average, about 70% of the total Fe in surface waters was found to be particulate.The average concentrations of dissolved Zn, Cd and Cu were found to be rather homogeneous in the water column but showed a relatively high variability with time. A simplified model on trace-metal uptake by phytoplankton indicates no significant change in dissolved metal concentrations during the period of investigation. On average, only 1.7% Zn, 3.3% Cd and 9.8% Cu of the total metal concentrations were found in particulate form. SPM analyses showed significant correlations of Zn, Cd and Cu with Fe, indicating that particulate iron is an important carrier for particulate trace metals in Baltic waters. 相似文献
11.
Klaus Kremling 《Marine Chemistry》1983,13(2):87-108
In June 1981, dissolved Zn, Cd, Cu, Ni, Co, Fe, and Mn were determined from two detailed profiles in anoxic Baltic waters (with extra data for Fe and Mn from August 1979). Dramatic changes across the O2H2S interface occur in the abundances of Cu, Co, Fe, and Mn (by factors of ?100). The concentrations of Zn, Cd, and Ni at the redox front decrease by factors between 3 to 5.Equilibrium calculations are presented for varying concentrations of hydrogen sulfide and compared with the field data. The study strongly supports the assumption that the solubility of Zn, Cd, Cu, and Ni is greatly enhanced and controlled by the formation of bisulfide and(or) polysulfide complexes. Differences between predicted and measured concentrations of these elements are mainly evident at lower ΣH2S concentrations.Cobalt proved to be very mobile in anoxic regions, and the results indicate that the concentrations are limited by CoS precipitation. The iron (Fe2+) and manganese (Mn2+) distribution in sulfide-containing waters is controlled by total flux from sediment-water interfaces rather than by equilibrium concentrations of their solid phases (FeS and MnCO3). The concentrations of these metals are therefore expected to increase with prolonged stagnation periods in the basin. 相似文献
12.
《Marine Chemistry》2001,76(3):175-187
Iron (Fe) is an essential element for the biochemical and physiological functioning of terrestrial and oceanic organisms, including phytoplankton, which are responsible for the primary productivity in the world's oceans. However, due to the low solubility of Fe in seawater, phytoplankton are often limited by their inability to incorporate enough Fe to allow for optimal growth rates in regions with dissolved Fe concentrations below 1 nM. It has been postulated that certain phytoplankton may produce compounds to facilitate the uptake of Fe from seawater to overcome this limitation. Dissolved Fe in the oceans is overwhelmingly complexed (>99%) by strong organic ligands that may control the uptake of Fe by microbiota; however, the identity, origin, and chemical characteristics of these organic chelates are largely unknown. Although it has been implied that some components of natural Fe-binding ligands are siderophores, no direct analyses of such compounds from natural seawater have been conducted. Here, we present a simple solid-phase extraction technique employing Biobeads SM-2 and Amberlite XAD-16 resins for concentrating naturally occurring dissolved iron-binding compounds from large volumes (>200 l) of seawater. Additionally, we report on the first successful determination of molecular weight size classes and preliminary iron-binding functional group characterization within those size classes for isolates collected from the surface and below the photic zone (150 m) in the central California coastal upwelling system. Electrochemical analyses using competitive ligand equilibration/adsorptive cathodic stripping voltammetry (CLE-ACSV) showed that isolated compounds had conditional Fe-binding affinities (with respect to inorganic iron—Fe′) of KFeL,Fe′cond=1011.5–1011.9 M−1, similar to purified marine siderophores produced in laboratory cultures and to the ambient Fe-binding ligands observed in seawater. In addition, 63% of the extracted compounds from surface-collected samples fall within the defined size range of siderophores (300–1000 Da). Hydroxamate or catecholate Fe-binding functional groups were present in each compound for which Fe binding was detected. These results illustrate that the functional groups previously shown to be present in marine and terrestrial siderophores extracted and purified from laboratory cultures are also present in the natural marine environment. These data provide evidence that a significant fraction of the organic Fe-binding compounds we collected contain Fe-binding functional groups consistent with biologically produced siderophores. These results provide further insight into characteristics of the Fe-binding ligands that are thought to be important in controlling the biological availability of Fe in the oceans. 相似文献
13.
Metal concentrations (Cd, Cr, Cu, Fe, Mn and Zn) were determined in seawaters and soft tissues of Chthamalus montagui from the northwest coast of Portugal during the four seasons of 2011. The main objectives of this work were to assess seasonal and spatial variations of metals in order to detect hot spots of contamination, to establish correlations between metals in coastal seawaters and C. montagui and to calculate metal bioaccumulation factors (BAFs) in each season. Metal concentrations in coastal seawaters ranged within Cd: 1.2–35 ng L?1; Cr: 15–87 ng L?1; Mn: 77–1763 ng L?1; Cu: 126–1819 ng L?1; Fe: 430–4048 ng L?1 and Zn: 2889–16867 ng L?1 and in C. montagui ranged for Cd: 0.39–1.98 mg kg?1; Cr: 0.45–3.13 mg kg?1; Cu: 0.93–5.70 mg kg?1; Mn: 2.2–20.4 mg kg?1; Fe: 135–707 mg kg?1 and Zn: 119–782 mg kg?1. Significant spatial and seasonal variations were found between: (i) metal concentrations in seawaters and C. montagui tissues; (ii) the distribution of metal concentrations in C. montagui tissues were Fe > Zn > Mn > Cu > Cr > Cd and (iii) C. montagui showed higher bioaccumulation factors for Fe and Cd than for Cu, Mn and Zn in all seasons. Regarding the metal concentrations accumulated in C. montagui tissues during each season of 2011, the ecological quality classifications of the NW coast of Portugal varied from “Class I–Unpolluted” to “Class III–Remarkably Polluted”. 相似文献
14.
M.J.A. Rijkenberg A.C. Fischer J.J. Kroon L.J.A. Gerringa K.R. Timmermans H.Th. Wolterbeek H.J.W. de Baar 《Marine Chemistry》2005,93(2-4):119-129
An iron enrichment experiment, EisenEx, was performed in the Atlantic sector of the Southern Ocean during the Antarctic spring of 2000. Deck incubations of open ocean water were performed to investigate the influence of ultraviolet B (UVB: 280–315 nm) and ultraviolet A (UVA: 315–400 nm) on the speciation of iron in seawater, using an addition of the radioisotopes 59Fe(III) (1.25 nM) or 55Fe(III) (0.5 nM). Seawater was sampled inside and outside the iron-enriched region. The radioisotopic Fe(II) concentration was monitored during daylight under three different light conditions: the full solar spectrum (total), total minus UVB, and total minus UVB+UVA. A distinct diel cycle was observed with a clear distinction between the three different light regimes. A clear linear relationship was found for the concentration of radioisotopic Fe(II) versus irradiance. UVB produced most of the Fe(II) followed by UVA and visible light (VIS: 400–700 nm), respectively. UVB produced 4.89 and 0.69 pM m2 W−1 radioisotopic Fe(II) followed by UVA with 0.33 and 0.10 pM m2 W−1 radioisotopic Fe(II) and VIS with 0.04 and 0.03 pM m2 W−1 radioisotopic Fe(II). 相似文献
15.
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
16.
We report a simplified synthesis, and some performance characteristics, for 8-hydroxyquinoline (8-HOQ) covalently bonded to a chemically resistant TosoHaas TSK vinyl polymer resin. The resin was used to concentrate trace metals from stored, acidified seawater samples collected from Jellyfish Lake, an anoxic marine lake in the Palau Islands. The Mn, Fe, and Zn profiles determined from the 8-HOQ resin extraction were similar to those determined using Chelex-100 resin. The Zn and Cd profiles did not exhibit removal by sulfide “stripping” in contrast to other anoxic marine basins. The profiles of Co and Ni also exhibited elevated concentrations in the anoxic hypolimnion. The solution speciation and saturation states for the metals were calculated using revised metal-bisulfide stability constants. The calculations suggest that the MS(HS)− species dominates the solution speciation for Mn, Co, Ni, Zn, Cd, and Pb. Cu(I) is modeled as the CuS− or Cu(HS)2− species, while Fe(II) behaves as the free Fe2+ cation. The Mn, Co, Ni, Cu and Cd concentrations appeared to be at least 10-fold undersaturated, while the Fe(II), Zn, and Pb concentrations were close to saturation with respect to their metal sulfides. 相似文献
17.
Arrigo A. Cigna 《Ocean Science Journal》2006,41(4):261-290
The concentrations of man made radionuclides in surface seawater since early ′60s are here reported as measured in Italy and
Japan. Most of the data refers to90Sr and137Cs, but occasionally the concentrations of89Sr and134Cs in some Italian samples are also given. The main sources of man made radionuclides were the global fallout produced by
the nuclear weapon tests and the Chernobyl accident. The respective contributions to the contamination of surface seawater
around both countries are discussed. 相似文献
18.
The stability constants of the ion pairs NaSO4?, KSO4?, MgSO4?, CaSO4, MgCl+ and CaCl+ were determined at 25°C and 0.7 M formal ionic strength, by measuring the solubility of gypsum (CaSO4 · 2H2O) in different media. The media used contained one or two of the following electrolytes: NaCl, KCl, MgCl2, NaClO4, Mg(ClO4)2, Na2SO4. Values for the stability constants are 1.22, 1.84, 12.3, 30.6, 0.48 and 1.20 M?1, respectively, and the solubility product for gypsum is 2.87 · 10?4M2. The distribution of the main constituents of seawater was calculated using these results and the values of the carbonate and bicarbonate constants given by Dyrssen and Hansson (1972–1973). The solubility of gypsum in seawater as calculated and determined experimentally was 21.43 mM and 21.10 mM, respectively. 相似文献
19.
Yoshio Sato 《Journal of Oceanography》1989,45(4):270-278
At the Minamichita Beach Land (Mihama-cho, Aichi, Japan), seawater is pumped up from underground and is supplied to aquaria. The underground seawater containsca. 2 ppm of Fe (II), 0.1 ppm of Mn (II) and a little dissolved oxygen. Iron oxide is formed in the seawater when aerated. The oxidation rate of Fe (II) was measured to be 1.4×1014 mol–3
l
3 min–1, which is comparable to the lowest values in the literature. The slow rate of Fe (II) oxidation obtained here can be attributed to the presence of organically bound iron in the seawater. The distribution coefficient of cations between seawater and iron oxide phase was in the order of Cu>Ni>Co>Cd>Mn, which is consistent with that predicted from their hydrolysis constants. The adsorption affinity sequence of oxyanions was phosphate >vanadate> molybdate. The difference in phosphate from the prediction of the adsorption theory was attributed to the formation of ferriphosphate on the oxide surface. On the basis of these data, the limitation and usefulness in the application of the distribution coefficients to marine environments were discussed. 相似文献
20.
Yasuo Nakamura 《Journal of Oceanography》1990,46(3):84-95
In order to assess the roles of Fe and Cu in outbreaks ofChattonella antiqua red tide, concentrations of these metals in the surface seawater were monitored around the Ie-shima Islands in the Seto Inland Sea during the summers of 1986–1988. Bioassay of the surface seawater with respect to Fe and Cu was also conducted using a cultured strain ofC. antiqua.Concentrations of Fe and Cu in the filtered seawater (FeF and CuF) were in the range of 3.9–10.0 and 9.3–11.2 nM, respectively. The bioassay with respect to Fe revealed that Fe at the surface layer was usually insufficient to support the maximum growth rate ofC. antiqua, except whenC. antiqua was dominant in the field. However, correlations between FeF and the growth rate of the control cultures (Fe, EDTA=not enriched; N, P, B12=enriched at optimum levels) were not apparent, probably because FeF did not reflect the concentration of available Fe.The bioassay with respect to Cu was coupled with the CuF values obtained. The results indicated that Cu at the surface layer was detoxified by complexation with natural organic ligand(s), and that pCu (=minus log of cupric ion activity) was 11.5–11.7, optimum for the growth ofC. antiqua, throughout the survey period. It is suggested that Fe, but not Cu, is a potentially important factor in regulating the natural populations ofC. antiqua in the Seto Inland Sea. 相似文献