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1.
We discuss the voltammetric methods that are used to assess metal–organic complexation in seawater. These consist of titration methods using anodic stripping voltammetry (ASV) and cathodic stripping voltammetry competitive ligand experiments (CSV-CLE). These approaches and a kinetic approach using CSV-CLE give similar information on the amount of excess ligand to metal in a sample and the conditional metal ligand stability constant for the excess ligand bound to the metal. CSV-CLE data using different ligands to measure Fe(III) organic complexes are similar. All these methods give conditional stability constants for which the side reaction coefficient for the metal can be corrected but not that for the ligand. Another approach, pseudovoltammetry, provides information on the actual metal–ligand complex(es) in a sample by doing ASV experiments where the deposition potential is varied more negatively in order to destroy the metal–ligand complex. This latter approach gives concentration information on each actual ligand bound to the metal as well as the thermodynamic stability constant of each complex in solution when compared to known metal–ligand complexes. In this case the side reaction coefficients for the metal and ligand are corrected. Thus, this method may not give identical information to the titration methods because the excess ligand in the sample may not be identical to some of the actual ligands binding the metal in the sample.  相似文献   

2.
土壤样品中贵金属活动态提取技术   总被引：6，自引：6，他引：0  
介绍了土壤样品中贵金属铂、钯、金的水提取态、黏土吸附态与可交换态、有机质结合态以及铁锰氧化物结合态等不同相态的提取方法与测定方法。方法检出限为铂0.03 ng/g,钯和金0.01 ng/g。实验了铂、钯、金活动态金属各种提取液介质中痕量贵金属的稳定性、固-液分离方法、提取温度的影响及提取液的处理方法。通过在南非隐伏铂钯矿或矿化区的试验,结果表明所圈定的异常与实际矿(化)体相符,为识别隐伏贵金属铂钯矿床提供了有效信息,对寻找隐伏矿床具有一定的指导意义。  相似文献   

3.
Although many bioessential metals are scarce in natural water and rock systems, microbial secretion of high-affinity ligands for metal extraction from solid phases has only been documented for Fe. However, we have discovered that Mo is extracted from a silicate by a high-affinity ligand (a possible “molybdophore”) secreted by an N2-fixing soil bacterium. The putative molybdophore, aminochelin, is secreted as a siderophore under Fe-depleted conditions, but is also secreted under Fe-sufficient, Mo-depleted conditions. Presumably, molybdophore production facilitates uptake of Mo for use in Mo enzymes. In contrast, an Fe-requiring soil bacterium without a special Mo requirement only enhances the release of Fe from the silicate. Fractionation of Mo stable isotopes during uptake to cells may provide a “fingerprint” for the importance of chelating ligands in such systems. Many such metal-specific ligands secreted by prokaryotes for extraction of bioessential metals, their effects on Earth materials, and their possible utility in the recovery of economic metals remain to be discovered.  相似文献   

4.
《Applied Geochemistry》2007,22(8):1636-1645
The ecological roles of dissolved organic matter (DOM) in seawater have not been well understood. One definite function of DOM stems from its complexation ability with trace metals under the conditions of seawater. A chemical complexation model of the marine system was introduced in order to clarify the ecological roles of strong organic ligands in DOM related to the acquisition of bioactive metals (Cu, Fe and Zn) by phytoplankton, assuming that two types of strong organic ligands coexist in oceanic DOM and complexes with bioactive metals. The results reveal that the weaker organic ligand, rather than the stronger one, plays a significant role in the reduction of Cu toxicity for phytoplankton growth. It is suggested that the presence of reactions with Cu that are competitive to the strong organic ligand causes extremely low Fe concentrations in seawater and leads to Fe deficiency for phytoplankton growth. Therefore, it is concluded that the strong ligands in DOM play a chemical role in controlling free ion concentration levels of bioactive metals in the marine environment.  相似文献   

5.
We discuss the voltammetric methods that are used to assess metal-organic complexation in seawater. These consist of titration methods using anodic stripping voltammetry (ASV) and cathodic stripping voltammetry competitive ligand experiments (CSV-CLE). These approaches and a kinetic approach using CSV-CLE give similar information on the amount of excess ligand to metal in a sample and the conditional metal ligand stability constant for the excess ligand bound to the metal. CSV-CLE data using different ligands to measure Fe(III) organic complexes are similar. All these methods give conditional stability constants for which the side reaction coefficient for the metal can be corrected but not that for the ligand. Another approach, pseudovoltammetry, provides information on the actual metal-ligand complex(es) in a sample by doing ASV experiments where the deposition potential is varied more negatively in order to destroy the metal-ligand complex. This latter approach gives concentration information on each actual ligand bound to the metal as well as the thermodynamic stability constant of each complex in solution when compared to known metal-ligand complexes. In this case the side reaction coefficients for the metal and ligand are corrected. Thus, this method may not give identical information to the titration methods because the excess ligand in the sample may not be identical to some of the actual ligands binding the metal in the sample.  相似文献   

6.
Fluidized-bed technology has established itself as a major processing technique in the non-ferrous metal industry. The technique is being commercially used or is being developed towards commercial use in ore separation and beneficiation, drying, calcining, roasting, metal extraction and refining, and metal and alloy treatment. This paper describes briefly and discusses the use of fluidization in these different stages. The discussion extends to certain design considerations and the scale-up problem. The problems associated with conducting the different processes are discussed.The pyrometallurgical processes, using fluidized beds, have been well established without significant problems for most of the non-ferrous metals. The use of fluidized beds is being applied to a wide field of different metal and alloy treatment processes.  相似文献   

7.
Group B metals, such as Hg, Cu, Ag, Pb and Cd bind strongly to reduced inorganic and organic S(II−) ligands. These S(II−) ligands, stable in oxic waters for significant periods of time, occur at the <1–100 s nM concentrations. It is hypothesized that S(II−) ligands are stabilized as Cu–S molecules associated with organic matter by multi-ligand binding or in nano-pore encapsulations in organic matter. S(II−) ligands are estimated by two methods: purge/trap analysis as Cr-reducible sulfide (CRS), and strong ligand (SLT) from a competitive ligand titration with Ag(I). The CRS/SLT ratio is nearly one for selected samples. CRS correlates reasonably well (r2 ∼ 0.5) with organic C with a slope of 14.6 nM per mg C. The conditional binding constant of Ag–SL is 11.3 for effluent associated with waste-water and decreases for river waters from about 12–8.8 as the strong sites are occupied with Ag(I).  相似文献   

8.
In order to evaluate thermodynamic speciation calculations inherent in biotic ligand models, the speciation of dissolved Cd, Cu, Pb, and Zn in aquatic systems influenced by historical mining activities is examined using equilibrium computer models and the diffusive gradients in thin films (DGT) technique. Several metal/organic-matter complexation models, including WHAM VI, NICA-Donnan, and Stockholm Humic model (SHM), are used in combination with inorganic speciation models to calculate the thermodynamic speciation of dissolved metals and concentrations of metal associated with biotic ligands (e.g., fish gills). Maximum dynamic metal concentrations, determined from total dissolved metal concentrations and thermodynamic speciation calculations, are compared with labile metal concentrations measured by DGT to assess which metal/organic-matter complexation model best describes metal speciation and, thereby, biotic ligand speciation, in the studied systems. Results indicate that the choice of model that defines metal/organic-matter interactions does not affect calculated concentrations of Cd and Zn associated with biotic ligands for geochemical conditions in the study area, whereas concentrations of Cu and Pb associated with biotic ligands depend on whether the speciation calculations use WHAM VI, NICA-Donnan, or SHM. Agreement between labile metal concentrations and dynamic metal concentrations occurs when WHAM VI is used to calculate Cu speciation and SHM is used to calculate Pb speciation. Additional work in systems that contain wide ranges in concentrations of multiple metals should incorporate analytical speciation methods, such as DGT, to constrain the speciation component of biotic ligand models.  相似文献   

9.
Ethylenediaminetetraaceticacid (EDTA) has been proven to be an efficient soil washing liquid to remove metal contaminants from soils. However, EDTA may cause secondary pollution due to its low biodegradability if it is not recycled or destroyed in the washing process. Thus, it is necessary to recycle and recover EDTA for sustainable use. In this paper, the extracting performance of fresh EDTA was firstly studied as a function of EDTA concentration, liquid/sediment (L/S) ratio and pH of the solution, and also extraction time. Then sodium tetraethylenepentamine-multi dithiocarbamate (TEPA-DTC), a heavy metals capturing agent, was synthesized on the base of the research of LIU-Lihua. Compared with Na2S and DDTC, TEPA-DTC shows strong chelating capacity, because it has functional groups of dithiocarbamate that could strongly chelate heavy metals and capture metal ions from Me-EDTA to form precipitates, allowing us to reclaim the EDTA during the process of soil washing. Three divalent heavy metals were investigated (Pb, Cd, and Cu). These three metals could almost precipitate completely with TEPA-DTC under the dosage of 300 mg/l, and EDTA was regenerated. The recovered EDTA was used again in three cycles of soil washing, and the amount of heavy metals extracted just slightly decreased each cycle.  相似文献   

10.
Deep-sea ferromanganese deposits contain a wide range of economically important metals. Ferromanganese crusts and nodules represent an important future resource, since they not only contain base metals such as Mn, Ni, Co, Cu and Zn, but are also enriched in critical or rare high-technology elements such as Li, Mo, Nb, W, the rare earth elements and yttrium (REY). These metals could be extracted from nodules and crusts as a by-product to the base metal production. However, there are no proper separation techniques available that selectively extract certain metals out of the carrier phases. By sequential leaching, we demonstrated that, except for Li, which is present in an easily soluble form, all other high-tech metals enriched in ferromanganese nodules and crusts are largely associated with the Fe-oxyhydroxide phases and only to subordinate extents with Mn-oxide phases. Based on this fact, we conducted selective leaching experiments with the Fe-specific organic ligand desferrioxamine-B, a naturally occurring and ubiquitous siderophore. We showed by leaching of ferromanganese nodules and crusts with desferrioxamine-B that a significant and selective extraction of high-tech metals such as Li, Mo, Zr, Hf and Ta is possible, while other elements like Fe and the base metals Mn, Ni, Cu, Co and Zn are not extracted to large extents. The set of selectively extracted elements can be extended to Nb and W if Mn and carbonate phases are stripped from the bulk nodule or crust prior to the siderophore leach by e.g. a sequential leaching technique. This combination of sequential leaches with a siderophore leach enhanced the extraction to 30–50% of each Mo, Nb, W and Ta from a mixed type Clarion-Clipperton Zone (CCZ) nodule and 40–80% from a diagenetic Peru Basin nodule, whilst only 5–10% Fe and even less Mn are extracted from the nodules. Li is extracted to about 60% from the CCZ nodule and a maximum of 80% Li is extracted from the Peru Basin nodule.Our pilot work on selective extraction of high-tech metals from marine ferromanganese nodules and crusts showed that specific metal-binding organic ligands may have promising potential in future processing technologies of these oxide deposits.  相似文献   

11.
Partitioning of heavy metals in surface Black Sea sediments   总被引：1，自引：0，他引：1  
Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.  相似文献   

12.
Excessive heavy metal content in sandy soils poses risk to human health and the environment. The rapid expansion of urban areas makes it imperative to manage contaminated sites so that land can be reclaimed for beneficial purposes. Several methods have been proposed to control the leaching of heavy metals from contaminated soils. In this study, four techniques for mobilization and immobilization of metals in sandy soil were compared. The assessed mobilization techniques included chemical extraction using aqueous solutions of acids and chelating agents as well as biochemical extraction using sulfur-oxidizing microorganisms. The evaluated immobilization techniques included lime-cement-pozzolan stabilization and natural-zeolite stabilization. The immobilization techniques do not involve removing metals from soil and instead focus on addition of substances to the soil that alter its composition, volume, and properties. On the other hand, mobilization techniques entail the removal of metals from soil and changes in the soil properties. The findings confirmed that both mobilization and immobilization are effective in controlling the leaching of metals from sandy soils and thereby minimize the risk to the environment and human health. However, the appropriate technique for application at a given site should be chosen on a case-by-case basis, while accounting for the economic and technical feasibility, the necessary level of cleanup, and effect of residual metals on human health and the environment.  相似文献   

13.
The sharp concentration peak of the metals Cu, Cd and Zn at the redoxcline of the Framvaren Fjord, Norway, is described as an effect of chelation/complexation with organic ligands. The most dominating ligand is 2-mercaptobenzothiazole (MBT), which binds with a 2 : 1 ligand to metal stoichiometric ratio. MBT has the highest concentrations at the vicinity of the redoxcline where the oxidation of sulfide to elemental sulfur and sulfate is most extensive. We suggest the production being caused by sulfide oxidizing bacteria as we have not been able to detect MBT in pure cultures of sulfate reducing bacteria. Ni does not exhibit the same distribution as the other three metals due to lower preference for coordination with S and N donor atoms and a much lower rate for loss of water than Cu, Cd and Zn.  相似文献   

14.
We used elemental carbon, nitrogen, hydrogen and sulfur as well as ratios of hydrogen and nitrogen with total organic carbon for investigation of source and conditions of organic matter in alluvial Danube sediments. We also determined the pseudo total concentrations of metals presented as a sum of extracted concentration after five sequential extraction steps. The pseudo total metal concentrations were found to be (mg kg−1) for Mn, 666; Fe, 25,852; Mg, 16,193; K, 2,063; Ni, 32.4; Zn, 72.2; Pb, 15.0; Cu, 26.0 and for Cr, 15.9. Correlation analysis and two multivariate analysis methods (principal component and cluster analysis) were helpful in determining the associations between the pseudo total extracted fractions of metals and with elemental carbon, hydrogen, nitrogen, sulfur, total inorganic and organic carbon. These correlations will help us to identify substrates of trace metals in different oxic/anoxic conditions. The correlation results of the trace metals and Fe, K, Mg and Mn suggest their adsorption, mainly onto Fe and Mn (hydro)oxides and K alumosilicates, whereas correlations of metals with sulfur indicate that they were precipitated as Fe-sulfides.  相似文献   

15.
Heavy metals are toxic elements that have hazardous effect on the environment. They cause soil pollution as a result of their toxicity, potential reactivity, and mobility in soils. There are so many methods for the measurement of heavy metal concentrations in soils and aquatic systems. The traditional methods used for detecting heavy metal distribution in soil involve laboratory analysis and raster sampling. Both of them are expensive and time-consuming for large areas. Remote sensing techniques are used for obtaining the earth’s surface information, and these techniques have been used in the investigations of heavy metal distributions in preliminary analysis of soils as a rapid method. Today, near-infrared reflectance spectroscopy (NIRS) of soil characteristics has been of interest as a significant object. The present investigation is focused on the detection of heavy metals in contaminated soils by the application of reflectance spectroscopy in the spectral range of 350 to 2500 nm. This study also discusses the circumstances of the applied current methods for the detection and estimation of arsenic (As), cadmium (Cd), nickel (Ni), and lead (Pb) in contaminated agricultural soils. In the first part of laboratory spectroscopy, estimations were done using heavy metal reflectance spectroscopy and partial least square regression (PLSR) approaches, while in the second part, the heavy metal estimations were done using soil organic carbon reflectance spectroscopy through the PLSR approaches. Similar to the tasks above, estimations of As, Cd, Ni, and Pb by using Landsat 8 images were done in the forms of direct and indirect methods and the distribution of heavy metals in the study area was determined. Finally, the results obtained using direct and indirect methods were compared with the wet chemical measurements of heavy metals and organic carbon. It was found that although the direct detection of heavy metals using the images of Landsat 8 produced more accurate results than the indirect detections, the results obtained from laboratory spectroscopy corresponded more with the results from atomic adsorption spectroscopy. On the other hand, based on the fact that the soil has a complex content, the use of nonlinear methods, such as artificial neural networks in predicting soil heavy metal contents, could be regarded as a trusted method.  相似文献   

16.
The form or speciation of a metal in natural waters can change its kinetic and thermodynamic properties. For example, Cu(II) in the free ionic form is toxic to phytoplankton, while copper complexed to organic ligands is not toxic. The form of a metal in solution can also change its solubility. For example, Fe(II) is soluble in aqueous solutions while Fe(III) is nearly insoluble. Natural organic ligands interactions with Fe(III) can increase the solubility by 20-fold in seawater. Ionic interaction models that can be used to determine the activity and speciation of divalent and trivalent metals in seawater and other natural elements will be discussed. The model is able to consider the interactions of metals with the major (Cl-, SO4 2-, HCO3 -, CO3 2-, Br-, F-) and minor (OH-, H2PO4 -, HPO4 2-, PO4 3-, HS-) anions as a function of temperature (0 to 50 °C), ionic strength [0 to 6 m (m = mol kg-1)] and pH (1 to 13). Recently, it has been shown that many divalent metals are complexed with organic ligands. Although the composition of these ligands is not known, a number of workers have used voltammetry to determine the concentration of the ligand [L n ] and the stability constant (K ML) for the formation of the complex  相似文献   

17.
Heavy metal and organic pollutants in sediments along the coastal zone of southeastern China have been investigated. Sediment samples are retrieved from three depositional environments: coast, estuary, and tide-affected river mouth. The relative abundance of heavy metal and organic pollutants is related to their geochemical properties as well as depositional environments and anthropogenic discharge. Based on a sequential extraction method, it is revealed that anthropogenic Pb, Cr, Cu, and Cd are mainly bound to Fe–Mn oxides, suggesting that adsorption and co-precipitation of Fe–Mn oxides are in the control of their transfer processes from water column to sediment. Heavy metal bound to carbonates is also an important pool especially for Cd, Mn, and Pb. The main organic pollutants found in the study area include petroleum-related alkanes, phthalic acid ester, organic silicon, chlorophenol, phenyl ether, and amine. The accumulation of heavy metals and organics in surficial sediments has a decrease tendency from estuarine environment to coastal environment and to tide-affected river mouth.  相似文献   

18.
Air-sea interfacial solutions have characteristically high concentrations of trace metals, microorganisms, organic compounds, and solids relative to bulk solutions. The potential for the chemical interaction of an array of trace metals in the interfacial regions with complexing organic ligands and adsorbing solid surfaces has been evaluated through the use of an equilibrium computer model. Computations suggest that higher interfacial accumulations of copper and lead may occur relative to cadmium and mercury. These results are found to be generally compatible with available field data describing trace metal interfacial accumulation. The forms of metals found to be partitioned between bulk and interfacial solutions are consistent with the hypothesis that solid surface adsorption and dissolved organic complexation reactions bring about metal enrichment at the surface microlayer.  相似文献   

19.
This paper presents a scheme of analysis for bottom sediments based on inductively coupled plasma-atomic fluorescence spectrometry and arc discharge atomic emission spectrometry combined with instrumental pyrolysis and gas chromatographic methods (head space analysis) for determining organic matter. The experimental investigation was performed on bottom sediments of the Kuybyshev and Ivankovo reservoirs on the Volga River, used as a drinking water supply. The selective sample dissolution method followed by the inductively coupled plasma-atomic fluorescence spectrometry liquid phase analysis and the arc discharge atomic emission spectrometry solid phase analysis was used to obtain quantitative information on heavy metal speciation in bottom sediments. In the present work we have taken the direct extraction scheme for analysis. It is shown that the proposed combination of instrumental methods is highly effective for revealing natural and anthropogenic components in the composition of organic matter, for conducting preliminary estimation of the binding of heavy metals with organic matter and for assessing activity of organic matter biochemical transformation. The proposed approach enlarges the capabilities for prediction and modelling of the processes in environmental-geochemical investigations.  相似文献   

20.
Three sediment cores were collected in the Scheldt, Lys and Spiere canals, which drain a highly populated and industrialized area in Western Europe. The speciation and the distribution of trace metals in pore waters and sediment particles were assessed through a combination of computational and experimental techniques. The concentrations of dissolved major and trace elements (anions, cations, sulfides, dissolved organic C, Cd, Co, Fe, Mn, Ni, Pb and Zn) were used to calculate the thermodynamic equilibrium speciation in pore waters and to evaluate the saturation of minerals (Visual Minteq software). A sequential extraction procedure was applied on anoxic sediment particles in order to assess the main host phases of trace elements. Manganese was the most labile metal in pore waters and was mainly associated with carbonates in particles. In contrast, a weak affinity of Cd, Co, Ni, Pb and Zn with carbonates was established because: (1) a systematic under-saturation was noticed in pore waters and (2) less than 10% of these elements were extracted in the exchangeable and carbonate sedimentary fraction. In the studied anoxic sediments, the mobility and the lability of trace metals, apart from Mn, seemed to be controlled through the competition between sulfidic and organic ligands. In particular, the necessity of taking into account organic matter in the modelling of thermodynamic equilibrium was demonstrated for Cd, Ni, Zn and Pb, the latter element exhibiting the strongest affinity with humic substances. Consequently, dissolved organic matter could favour the stabilization of trace metals in the liquid phase. Conversely, sulfide minerals played a key role in the scavenging of trace metals in sediment particles. Finally, similar trace metal lability rankings were obtained for the liquid and solid phases.  相似文献   

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