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1.
Paul Schindler's early work on the acid-base chemistry of oxides was instrumental for the development of the concept of surface complexation. This approach has not only been important in establishing a theory on the adsorption of metal ions and ligands as a function of pH and solution variables, but has become essential in establishing surface speciation (coordinative structural and electronic arrangement at the solidwater interface) which in turn determines surface reactivity. The factors that affect dissolution of Fe(III) (hydr)oxides and inhibition of dissolution are discussed. A few examples for the inhibition of reductive and ligand-promoted dissolution by binuclear complexes of oxoanions (phosphate, borate) and of protonpromoted dissolution by Cr(III) are given.  相似文献   

2.
Cr(III) sorbed at the solid/water interface of latex and hectorite was studied by ESR spectroscopy in the presence of different inorganic ligands. The ESR spectra of the surface obtained in the presence of selenite, phosphate and fluoride can be explained in terms of ternary surface complex formation. This is contrasted by the behaviour of sulfate and selenate ions which were found to have no effect on the ligand field of Cr(III), either in the adsorbed state or in solution.  相似文献   

3.
4.
The chemical speciation of dissolved copper was investigated in waters from the limno-corrals of the MELIMEX project and compared with speciation data from other Swiss lakes. Copper is complexed primarily by organic ligands having molecular sizes between 104 and 103 daltons. The mean concentration of the ligands is approximately 5×10−7 mole/mg DOC. The conditional stability constants (pH=8.8) are about 1011. An increased metal load did not induce an increase of binding ligands. A comparison of calculated Cu2+ concentration with corresponding copper contents in the biomass leads to the conclusion that organic ligands and pH are the most important factors in deciding the biological availability of copper. However the sorption capacity of the biomass depends as well on the variety of plankton species.  相似文献   

5.
Continental inputs of copper via rivers and sewage into the Vigo Ria were evaluated. The main fluvial input is not contaminated and the most degraded discharges occur on the southern margin of the middle ria. Continental inputs of copper and ligands to the ria are dominated by sewage treatment plants (136 mol Cu day(-1), 124 mol L day(-1)) supported by rivers (15 mol Cu day(-1), 21 mol L day(-1)). The dissolved fraction is the main channel of discharge for rivers (66%) with particulate matter being predominant in sewage (63%). Dissolved copper is organically complexed both in rivers (99.8%) and sewage (99.9%). This minor difference may be attributed to the fact that the stability of sewage complexes is greater than those in rivers. Moreover, ligand concentrations are higher in sewage than in rivers. Thus, the natural continental inputs of copper and ligands into the ria are magnified by anthropogenic inputs (5-15 and 3-5 times higher for copper and ligands, respectively).  相似文献   

6.
Various synthetic compounds are frequently discharged into the environment via human activities. Among them, certain contaminants may disrupt normal physiological functions of wildlife and humans via interactions with nuclear receptors. To protect human health and the environment, it is important to detect environmental ligands for human nuclear receptors. In this study, yeast-based reporter gene assays were used to investigate the occurrence of xenobiotic ligands for retinoid X receptors (RXR) and thyroid hormone receptors (TR) in the aquatic environment of Taiwan. Experimental results revealed that RXR agonist/antagonist activity was detected in river water and sediment samples. In particular, high RXR agonist/antagonist activity was found in the samples collected near river mouths. Additionally, few samples also elicited significant TR antagonist activity. Our findings show that the aquatic environment of Taiwan was contaminated with RXR and TR ligands. Further study is necessary to identify these xenobiotic RXR and TR agonists and antagonists.  相似文献   

7.
[Cu2+] and Cu complexation parameters in some selected freshwater systems in Switzerland were determined by the technique of ligand-exchange and DPCSV. Results from the water columns of some eutrophic and oligotrophic lakes are presented and compared to small acid lakes. Cu is strongly complexed by organic ligands which with very high stability constants at low concentrations are probably biologically produced, as indicated by the seasonal variations in the eutrophic lakes and by the relationship between Cu complexation and algal activity in the eutrophic (pCu=15–16), oligotrophic (pCu=13–14) and acidic (pCu=9–10) lakes. The extent of Cu complexation in river waters was generally lower than in the eutrophic lakes, at similar DOC levels. No obvious correlation between Cu complexation and DOC was observed, indicating that Cu complexing ligands are specific organic compounds.  相似文献   

8.
Europium redox equilibria in aqueous solution   总被引:6,自引:0,他引:6  
Thermochemical data and recent advances in theoretical aqueous solution chemistry enable prediction of the relative stabilities of aqueous Eu2+ and Eu3+ over a wide range of temperatures and pressures. At low temperatures, near earth surface conditions, the aqueous geochemistry of europium should be dominated by the trivalent state, except possibly in the most reducing, alkaline pore waters of anoxic marine sediments. However, at temperatures greater than about 250°C and elevated pressures, divalent europium should predominate. Even with significant amounts of complexing, trivalent europium is not stable at elevated temperatures and pressures. Consequently, under most hydrothermal and metamorphic conditions, europium in aqueous solution should be divalent. At intermediate temperatures, around 100°C, significant activities of both Eu2+ and Eu3+, and related complexes, can occur in aqueous solutions, depending on the oxidation state and the pH of the solutions, and the activities of potential ligands such as sulfate, carbonate and chloride. The predicted stability of divalent europium in aqueous solution at elevated temperatures is consistent with the large positive europium anomalies in rare earth element patterns of high-temperature barites of hydrothermal and metamorphic origin reported by Guichard et al. [5] and with the observed depletion of europium as a result of high-temperature sericitization of feldspar-bearing assemblages discovered by Alderton et al. [1]. It is suggested that significant fractionation of europium relative to the other rare earth elements may take place during high-temperature hydrothermal alteration processes, such as in the mid-oceanic ridge systems, because of the expected stability of divalent europium during these processes.  相似文献   

9.
A mathematical model is presented for the calculation of the concentrations or activities of complex compounds in the thermodynamic equilibrium state. Ten central atoms and ten ligands which form 400 complexes at the most can be included in the model. Complex stability constants, total concentrations of the central atoms and ligands, temperature and pH-value constitute input quantities. Activity and temperature dependence of the stability constants are covered by respective subprogrammes. The model is tested by the migration rate of iron(II) within a sand-filled column with a cation-exchange capacity of 1 mval/100 g solid matter: If there is an excess of sulphate, the iron(II)-breakthrough will be considerably earlier, the same holding for the EDTA-complex, whereas by means of EDTA the iron(II) bonded to the soil by ion exchange can be redissolved. In the batch experiment also the rate of oxidation of iron(II) is dependent on the degree of complexing. The model can be extended for dissolving, precipitation and redox processes.  相似文献   

10.
The contribution of organic bases to the alkalinity of the anoxic hypolimnetic water of a small lake has been studied. By means of potentiometric titrations the presence of a protolyte, best described as a one-protonic acid (HL) could be shown. The pka of HL was found to be 4.24±0.08 (3σ) and it reached a concentration of 0.4 mM close to the sediment surface. Because of precipitation reactions titration experiments could not be performed above pH≈6.8, but indications of additional bases having a pka >8were found. The results indicate the presence of low molecular weight carboxylic acids and free amino acids originating from bacterial decomposition of organic material. Polarographically measured Fe2+ concentrations, in situ pH measurements and various model ligands were used to assess the metal speciation in the hypolimnion. Although strong metal complexing agents such as citrate and glutamine may be present, the total concentrations of both Fe2+ (up to 0.6 mM) and ligands are too low to bind more than at maximum 20% of the ferrous iron.  相似文献   

11.
Seasonal dynamics of total concentrations and the main forms of occurrence of heavy metals (HM) in the water mass and bottom deposits (BD) are studied in the Priplotinnyi (Near-dam) Pool of the Kuibyshev Reservoir. In the near-bottom and interstitial waters, heavy metals are mostly found in the form of complex compounds with organic and mineral ligands; the proportions of these complexes and the dominant form in the above media change from season to season. The hard skeleton of bottom deposits contains a large store of heavy metals that can be a source of the secondary pollution of water masses.  相似文献   

12.
A preparative method was developed to sample dissolved organic carbon (DOC) and heavy metals (Ni, Mn) from polluted surface waters. Main focus was set on the preparative production of freeze‐dried samples mainly composed of organic ligands from heavy metal complexes. First characterizations were done in the aqueous phase. Finally, freeze‐dried samples provide stable organic matter for multiple characterizations. Acid mine drainage of the former mining area of Ronneburg (Germany) hold elevated concentrations of heavy metals and low concentrations of DOC. Municipal wastewater, passing the spoil pile, held elevated concentrations of DOC and low concentrations of heavy metals. Dissolved components smaller than 0.45 μm and larger than 1 nm were concentrated by nanofiltration. Organic heavy metal complexes were isolated from this solution by size‐exclusion chromatography (SEC). Different size classes of molecules were collected from the column effluent, depending on their elution time, and were characterized by UV spectroscopy, ICP‐OES, and DOC measurements. All samples held organic heavy metal compounds with different retention times. The organic heavy metal complexes in acid mine drainage had higher retention times than complexes from municipal wastewater. Most interestingly, we found different affinities of heavy metals to different size classes of DOC. This affinity of the heavy metals differs with size and origin of the DOC.  相似文献   

13.
Enzyme immunoassays profit from the unique properties of antibodies concerning their selectivity and affinity towards ligands, e.g. pesticides. The most commonly applied types belong to the class of competitive immunoassays with phase separation such as the ELISA. The principle is explained and illustrated using an atrazine assay as a representative example. Common error sources, especially cross-reactivities and matrix effects, are discussed. Interlaboratory tests demonstrate the presently available quality of enzyme immunoassays. An outlook is given on future developments.  相似文献   

14.
Numerous cold regions water flow and energy transport models have emerged in recent years. Dissimilarities often exist in their mathematical formulations and/or numerical solution techniques, but few analytical solutions exist for benchmarking flow and energy transport models that include pore water phase change. This paper presents a detailed derivation of the Lunardini solution, an approximate analytical solution for predicting soil thawing subject to conduction, advection, and phase change. Fifteen thawing scenarios are examined by considering differences in porosity, surface temperature, Darcy velocity, and initial temperature. The accuracy of the Lunardini solution is shown to be proportional to the Stefan number. The analytical solution results obtained for soil thawing scenarios with water flow and advection are compared to those obtained from the finite element model SUTRA. Three problems, two involving the Lunardini solution and one involving the classic Neumann solution, are recommended as standard benchmarks for future model development and testing.  相似文献   

15.
Domenico solution--is it valid?   总被引:1,自引:0,他引:1  
The Domenico solution is widely used in several analytical models for simulating ground water contaminant transport scenarios. Unfortunately, many textbook as well as journal article treatments of this approximate solution are full of empirical statements that are developed without mathematical rigor. For this reason, a rigorous analysis of this solution is warranted. In this article, we present a mathematical method to derive the Domenico solution and explore its limits. Our analysis shows that the Domenico solution is a true analytical solution when the value of longitudinal dispersivity is zero. For nonzero longitudinal dispersivity values, the Domenico solution will introduce a finite amount of error. We use an example problem to quantify the nature of this error and suggest some general guidelines for the appropriate use of this solution.  相似文献   

16.
针对描述非线性Rossby波的正压准地转位涡方程,设计了一个隐式差分迭代格式,通过数值解与精确解对比的方法,验证了差分迭代格式的精度和稳定性.首先将正压准地转位涡方程简化为Couette流方程,对比了Couette流精确解和数值解,验证了差分格式对线性方程数值计算的精度和稳定性;然后通过构造精确解和修改原方程的方法,验...  相似文献   

17.
Summary The frequency equation is derived for the propagation of Love waves in a two layered crust overlying an inhomogeneous half-space. While exact solutions of the differential equation involved are obtained in some particular cases, both an asymptotic series and the WKBJ approximations are discussed for the solution in the general case. The asymptotic series solution and the WKBJ solution are compared with each other and with the asymptotic expansion of the exact solution. There is a good agreement between various results. It is shown that some of the existing results can be derived as particular cases of the general results obtained in this investigation.  相似文献   

18.
19.
Ground water flow in karst terranes generally occurs in the solution channels of carbonate aquifers. A hydrogeologist may utilize borehole geophysical methods to identify these solution channels in aquifers. Two specific methods that are applicable in karst terrains are:
1. Natural gamma ray logging
2. Borehole caliper logging.
Gamma ray logging can detect the presence of inter-bedded strata in the main limestone unit, such as shale, which emit high levels of gamma radiation. Gamma ray logging can also detect clay deposits in solution channels that may act to restrict the flow of ground water. The areal extent of these rock strata or clay-filled solution channels can be determined when gamma ray logs are conducted at several borehole locations across the site of investigation.
Borehole caliper logging can be employed to determine the presences of solution channels within the aquifer when penetrated by a borehole. In addition, since shale layers and clay filling are less resistant than the surrounding limestone, the caliper log may detect both the presence and the thickness of shale or clay layers in the aquifer.
Gamma ray logs can be used in conjunction with caliper logs to provide data on the stratigraphic location and thickness of solution channels and clay and shale layers within a limestone aquifer. This information is valuable to the hydrogeologist performing investigations at sites located in limestone terranes because ground water flow preferentially occurs along solution channels.  相似文献   

20.
Through the Fourier-Bessel series expansion of wave functions,the analytical solution to the two-dimensional scattering problem of incidental plane P waves by circular-arc canyon topography with different depth-to-width ratio is deduced.Unlike other existing analytical solutions,in order to ensure that the analytical solution is valid for higher frequency incident waves,the asymptotic properties of cylindrical functions are in this paper introduced to directly determine the unknown coefficients of scattering waves,avoiding the solution of linear equation systems and corresponding numerical issues,which in turn expand the frequency band in which the analytical solution is valid.Comparison with other existing analytical solutions demonstrates that the proposed analytical solution is correct.Furthermore,the scattering effects of a circular-arc canyon on the incident plane P wave are analyzed in a comparatively broad frequency band.  相似文献   

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