海黍子和脆江蓠对重金属锌、镉富集的比较研究

采用室内培养实验方法,研究了褐藻海黍子(Sargassum muticum)和红藻脆江蓠(Gracilaria chouae)在不同质量浓度的锌和镉溶液里15 d,藻体的生长和体内金属离子含量的变化。结果表明:两种藻的生长速率与暴露溶液金属质量浓度呈负相关,藻体内积累金属离子的量和溶液的金属质量浓度呈正相关,藻体内金属离子的含量均在培养3 d后显著增加,且随着培养时间的延长而持续增加。海黍子和脆江蓠对重金属Zn~(2+)的富集能力明显高于对Cd~(2+)的富集能力,在相同条件下,海黍子对重金属Zn~(2+),Cd~(2+)的积累量明显高于脆江蓠。以上研究结果对利用藻类修复重金属污染的海洋水体能起到一定的指导和参考作用。     

Some geochemical controls on lead and barium concentrations in ferromanganese deposits

The Pb content of natural deep-sea ferromanganese deposits decreases with depth. This is commonly explained by assuming oxidation of Pb²⁺ and uptake as (Mn, Pb)O₂ in normally oxygenated shallow water, a process that is less likely to occur in deep water which is somewhat depleted in oxygen. This concept is discussed and rejected, both on theoretical grounds and based on experimental results of Pb²⁺ sorption by Mn oxides. Comparative sorption experiments on Mn oxides were carried out with Pb and Ba. It is shown that Pb is preferentially adsorbed by birnessite at $\text{pH}\text{? 4}$. The uptake ratio is, however, much lower than the relative enrichment factor in natural nodule material. Suggested explanations for this discrepancy are: influence of hydrostatic pressure and extent of hydrolysis of the cations at the pH of ocean water.     

Stoichiometry among bioactive trace metals in the Chukchi and Beaufort Seas

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.     

Simplified synthesis of an 8-hydroxyquinoline chelating resin and a study of trace metal profiles from Jellyfish Lake, Palau

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.     

锑原位掺杂SiO2@PDA-Sb复合材料修饰电极用于海水中Zn离子检测

本研究提出了一种用于检测海水中锌离子(Zn²⁺)含量的电化学检测方法。该方法首先应用水热法合成SiO₂@PDA-Sb复合材料,然后将该复合材料修饰到玻碳电极上制备SiO₂@PDA-Sb-Nafion/GCE,利用差分脉冲阳极溶出伏安法(DPASV)对珠江口海水水样中Zn²⁺进行测定。研究结果表明,Zn²⁺在SiO₂@PDA-Sb-Nafion/GCE上具有较强的溶出峰。在最优条件下,SiO₂@PDA-Sb-Nafion/GCE对Zn²⁺浓度在1～1 000 nmol/L范围内可实现灵敏、准确的检测,Zn²⁺的检测出限为0.71 nmol/L。加标回收率实验显示Zn²⁺加标回收率为93.19%～100.12%,表明该方法可应用于现场海水样品Zn²⁺测定。本方法具有电极制作简单、稳定性和抗干扰性良好,能够提高现有测定方法的检测限和精确度,在现场海水检测...     

Complexation of dimethylsulfide with mercuric ion in aqueous solutions

The tendency of dimethylsulfide (DMS) to form complexes with heavy metal ions in aqueous solutions and the factors that influence it have been investigated. Among five heavy metal ions examined (Cu²⁺, Cd²⁺, Zn²⁺, Pb²⁺ and Hg²⁺), only Hg²⁺ bound significantly with DMS in aqueous solutions in which Hg²⁺ concentration was increased to much higher levels than that of natural seawater. The complexation capacity of Hg²⁺ for DMS was influenced by pH and media. The affinity of Hg²⁺ for DMS was generally lower at high than at low pH, presumably due to the competition of hydroxide ion to form hydroxomercury species. In different solutions, the affinity of Hg²⁺ for DMS followed the following sequence: ultra-purified water > 35‰ NaCl solution > seawater. It seems apparent that chloride had a negative impact on the complexation of DMS by Hg²⁺, owing to the competition of chloride with DMS for complexing Hg²⁺. In addition, the affinity of Hg²⁺ for DMS in the bulk seawater appeared to be higher than that in the surface microlayer seawater. The tendency of Hg²⁺ to form complexes with DMS in aqueous solution can be reduced by the presence of 2 mM amino-acid such as glycine, alanine, serine and cysteine, as these ligands give stable mercury complexes. However, the presence of 2 mM acetate in experimental solutions had no significant effect on the complexation of Hg²⁺ with DMS, even though this ligand has a relatively strong complexing capacity for Hg²⁺. Although mercury ions appeared to have a strong affinity for DMS, the concentration of mercury in seawater is too low to produce a great effect on the distribution of DMS in oceans.     

Stoichiometry among bioactive trace metals in seawater on the Bering Sea shelf

The distribution of Al, Mn, Fe, Co, Ni, Cu, Zn, Cd, and Pb in seawater was investigated on the Bering Sea shelf (56–64°N, 165–169°W) in September 2000. The unfiltered and filtered seawater samples were used for determination of total dissolvable (TD) and dissolved (D) metals (M), respectively. The TD-M concentrations were generally higher than in the Pacific Ocean. TD-Cd was highest in deep water of the outer shelf domain and dominated by dissolved species. The other TD-M were highest at stations close to the Yukon River delta and had higher fractions of labile particulate (LP) species that were obtained as the difference between TD-M and D-M. Dissolved Al, Ni, and Cu were characterized by input from the Yukon River. Dissolved Mn and Co showed maximums on the bottom of the coastal domain, suggesting influence of sedimentary Mn reduction. The correlations of D-Zn, D-Cd, and macronutrients indicated their distributions were largely controlled through uptake by microorganisms and remineralization from settling particles. All these three processes (river input, sedimentary reduction, and biogeochemical cycle) had an influence on the distribution of D-Fe. D-Pb was fairly uniformly distributed in the study area. The stoichiometry of D-M in the Bering Sea shelf showed enrichment of Co and Pb and depletion of Ni, Cu, Zn, and Cd compared with that in the North Pacific. The LP-M/LP-Al ratio revealed significant enrichment of the other eight metals relative to their crustal abundance, suggesting importance of formation of Fe–Mn oxides and adsorption of trace metals on the oxides.     

Measurement of manganese, zinc and cadmium complexation in seawater using Chelex ion exchange equilibria

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.     

Significance of oxides and particulate organic matter in controlling trace metal partitioning in a contaminated estuary

The sediment–water partitioning of radiolabelled Cd, Hg and Zn has been investigated along an estuarine salinity gradient using samples from the Mersey Estuary, UK. Partitioning was studied using untreated particles, and particles that had been extracted using either a reducing agent (NH₂OH.HCl–HOAc) or an oxidising agent (H₂O₂) in order to qualitatively evaluate the relative roles of Fe–Mn oxides and particulate organic matter (POM), respectively, on metal uptake. The extent of Cd partitioning between sediment and water, parameterised in terms of the distribution coefficient, K_D, exhibited a reduction with increasing salinity, regardless of whether or not particles had been digested. However, the magnitude of K_D decreased significantly following either chemical treatment, suggesting that both oxides and organic matter are important sorbents for Cd. The K_D for Hg in the presence of untreated particles increased with increasing salinity, and chemical reduction of the particles enhanced the uptake of Hg and reinforced this trend. Particle oxidation led to a significant reduction in the K_D for Hg, and uptake by the particles decreased with increasing salinity. These observations suggest that POM is considerably more important than Fe–Mn oxides in the removal of aqueous Hg, and that its presence is a prerequisite for enhanced sorption (or salting out) at elevated salinities. The salinity dependence of K_D for Zn displayed characteristics of both Cd (below salinities of about 5) and Hg (at greater salinities). However, the magnitude of K_D for Zn uptake was relatively insensitive to either chemical treatment, suggesting that oxides, POM, and residual phases contribute to the overall sorption of Zn by estuarine particles. Regression analyses of the metal partition data suggest that sorption to oxides and POM is nonadditive, and that the salinity dependence of metal partitioning results mainly from salinity-controlled interactions between metal and organic matter. Sequential extraction of metals bound to untreated and chemically treated particles in the partitioning experiments indicated that the exchangeability or lability of all metals increased on removal of either oxides or POM. This implies that sorption sites of relatively high energy are destroyed (or become less accessible), or sorption sites of relatively low energy are created (or become more accessible) on chemical treatment. These observations support a conceptual model for the particle surface whose integrity and binding properties are only maintained by the coexistence of and interaction between oxides and organic matter.     

Chelation of divalent metal ions by brown algal polyphenols

High-molecular-weight, nondialyzable polyphloroglucinols from the marine brown algae Ascophyllum nodosum and Fucus vesiculosus (Phaeophyceae, Fucales) chelate the divalent metal ions Sr²⁺, Mg²⁺, Ca²⁺, Be²⁺, Mn²⁺, Cd²⁺, Co²⁺, Zn²⁺, Ni²⁺, Pb²⁺ and Cu²⁺ in weakly acidic aqueous solution. Values of the relative selectivity coefficients k have been calculated relative to Mn²⁺; the ionotropic series with the algal polyphenols are similar to those with catechol and pyrogallol. These studies may serve as a guide for the examination of metal chelation by brown algal polyphenols both in situ and after exudation into seawater.     

Behavior of Zn<Superscript>2+</Superscript>, Cd<Superscript>2+</Superscript>, Ba<Superscript>2+</Superscript> and Pb<Superscript>2+</Superscript> cations in ferromanganese crusts from the Marcus Wake seamount (Pacific Ocean) in aqueous solutions of metal salts

The behavior of heavy-metal cations in ore minerals of cobalt-rich ferromanganese crusts from the Marcus Wake seamount in aqueous solutions of metal salts was studied in experiments. The Zn²⁺ and Cd²⁺ cations showed high reactivity and Ва²⁺ and Pb²⁺ showed low reactivity. It was found that Zn²⁺ and Cd²⁺ cations within the ore mineral composition are mainly absorbed (up to 66%) whereas Pb²⁺ and Ва²⁺ are chemically bound (up to 70%). Ore minerals in the crusts are characterized by sorption properties and high ionexchange capacity by these cations (1.94–2.62 mg-equiv/g). The capacity values by heavy-metal cations for ore minerals of the crusts from different areas of the Marcus Wake seamount are close to each other.     

Cadmium bioconcentration in the echinoid Paracentrotus lividus: Influence of the cadmium concentration in seawater

Uptake and loss kinetics of cadmium were studied in Paracentrotus lividus exposed for 24 d to different stable Cd concentrations (0 to 1.14 μg Cd l⁻¹) and ¹⁰⁹Cd tracer added to seawater. The whole-body uptake kinetics were linear over the time course of the experiment. The whole-body ¹⁰⁹Cd concentration factor was independent of the stable Cd concentration in ambient seawater. Bioconcentration of Cd in whole individuals and their body compartments was directly proportional to the Cd concentration added to the seawater. The echinoid digestive tract wall showed the highest degree of Cd uptake. Whole-body loss kinetics were described by a 2-component exponential equation. The loss kinetics were similar for each of the treatments examined. Cadmium was found to display a long biological half-life in echinoid tissues; the major fraction (73 to 85%) of the Cd taken up by echinoids was eliminated following a loss component whose biological half-life was of the order of 1 year, regardless of the absolute Cd concentration accumulated by the echinoid. Paracentrotus lividus is suggested as a valuable biomonitor of Cd, particularly where knowledge of Cd concentration variations over long-term is of interest.     

The distribution of Mn,Fe, Zn,Cd and Cu in Baltic seawater; a study on the basis of one anchor station

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.     

Cadmium and phosphate in coastal Antarctic seawater: Implications for Southern Ocean nutrient cycling

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

Inhibitory effects of divalent metal ions on liver microsomal 7-ethoxyresorufin O-deethylase (EROD) activity of leaping mullet

The purpose of the present study was to elucidate in vitro effects of Hg²⁺, Zn²⁺, Ni²⁺ and Cd²⁺ on cytochrome P4501A1 (CYP1A1) dependent EROD activities in leaping mullet liver microsomes. Fish captured from the most polluted part of Izmir Bay, had highly elevated EROD activities, and induced CYP1A1 protein levels as determined by Western blotting. Although all of the metal ions caused inhibition of the initial velocity of the reaction, Hg²⁺ and Cd²⁺ exhibited much higher inhibitory effect at lower concentrations and they were evidently more potent inhibitors than others. The inhibitor concentration giving 50% inhibition (IC₅₀ values) of Zn²⁺, Ni²⁺, Cd²⁺ and Hg²⁺ of initial EROD activity were 107, 16, 1.3 and 0.15 micromolar, respectively. Glutathione (GSH) at 0.5 mM final concentration, completely reversed Ni²⁺ and Cd²⁺ inhibition of EROD activity indicating the protective action of GSH.     

Influence of Salinity on pH and Aluminum Concentration on the Interaction of Acidic Red Soil with Seawater

Contamination of acidic red soil in the coastal areas of Okinawa Islands is a serious environmental problem. This study was conducted to examine the effects of the salinity on pH and aluminum concentration when the acidic red soil interacts with seawater. Acidic red soil from Gushikawa recreation center was fractionated into bulk soil, coarse sand and silt + clay. Different weights of each fraction were equilibrated with seawater solutions. The pH and concentrations of Al³⁺, Na⁺, K⁺, Ca²⁺ and Mg²⁺ were then analyzed in the extracts. The results showed a decreasing trend of pH with increasing soil to solution ratio while the extracted Al³⁺ revealed an increasing trend. The lowest pH values were 3.85, 4.06, 4.41, 4.66 and their corresponding highest Al³⁺ concentrations were 2.50, 1.01, 0.062 and 0.036 mmolL⁻¹ in the seawater extracts, one-tenth seawater extracts, one-hundredth seawater extracts and one-thousandth seawater solution extracts, respectively. Mostly, the concentrations of Na⁺, Ca²⁺, Mg²⁺ and especially K⁺ decreased with increasing soil weight in the high salinities but showed the opposite trend in the low salinity samples. Potassium concentration decreased by 39%, 53% and 40% in the seawater extracts, one-tenth and one-hundredth seawater extracts but increased by 200% in one-thousandth seawater extracts. The coincidence of the increase in Al³⁺ and H⁺ concentrations, and the decrease of Na⁺, K⁺, Ca²⁺ and Mg²⁺ concentrations in the solutions suggests ion exchange/adsorption, while the increased patterns, particularly at low salinity could be attributed to the dissolution of the species from the soils.     

Sorption of transition metals on manganese and iron oxides,and silicate minerals

Experiments of sorption of Mn, Co, Ni, Cu and Zn on manganese oxides, hydrated ferric oxide, Na-montmorillonite and treated red clay are carried out in connection with the mechanisms by which transition metals are removed from seawater in marine environments.The order of sorption affinities of transition metals for Na-montmorillonite, treated red clay and hydrated ferric oxide is Mn相似文献   

The behavior of Zn,Cd, Cu,Ni, Co,Fe, and Mn in anoxic baltic waters

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 O₂H₂S 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.     

THE EFFECT OF FOUR HEAVY METALS ON THE GROWTH RATE AND CHLOROPHYLL CONTENT OF Chaetoceros muelleri LEMMERMANN

Chaetoceros muelleri Lemmermann was cultured in solution of different concentrations of Cu2 , Pb2 , Zn2 and Cd2 , and in mixtures of any two of them. After 6 days the effect of these heavy metal cations on the growth rate and chlorophyll contents of the diatom were determined and an Opton microscope was used to observe the morphology and size of the cells.The experimental results show that the effects of toxicity of these four heavy metals on Chaetoceros muelleri are: Cu2 >Pb2 >Zn2 >Cd2 . However, the cells did not differ significantly in their morphology and size from the controled ones.In any of the mixed metals cultures, its growth rate came close to and was higher than that of the single metal culture of higher concentration.