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1.
Conditional surface binding constants and complexation capacities for Zn, Pb, Cd, and Cu were determined from surface titration experiments of heterogeneous natural aquatic particulate matter of different origin and composition. Metals and particles were evaluated in naturally occurring concentration ranges in river water.The adsorption of trace metals can be adequately described with a single conditional binding constant over a wide range of metal : particle ratios. Binding constants for aquatic particles at pH 8.0 are remarkably independent from particle composition and are specific for each metal: log Kads Zn = 8.39, log Kads Pb = 9.67, log Kads Cd = 8.61, log ads Cu = 9.84. From competition experiments with Ca and Pb we extracted a sorption coefficient for Ca of log Kads Ca = 2.5 (pH 8.0). Maximum surface binding capacities for all metal ions were found for particles containing high fractions of Mn-oxides which are associated with large specific surface areas. Generally, we found sorption capacities to decrease in the sequence Cu Pb, Zn > Cd.The experiments suggest that the conditional surface binding constants and complexation capacities are applicable to model trace metal adsorption in the concentration ranges of natural waters under conditions similar to the experiments. Results also imply that the chemical nature of particle surface sites is rather uniform in the intermediate concentration range or that the array of binding sites averages out differences in sorption strength over the prevailing concentration range of metal ions, respectively.  相似文献   

2.
Bacteria are very efficient sorbents of trace metals, and their abundance in a wide variety of natural aqueous systems means biosorption plays an important role in the biogeochemical cycling of many elements. We measured the adsorption of Cu(II) to Bacillus subtilis as a function of pH and surface loading. Adsorption edge and XAS experiments were performed at high bacteria-to-metal ratio, analogous to Cu uptake in natural geologic and aqueous environments. We report significant Cu adsorption to B. subtilis across the entire pH range studied (pH ∼2-7), with adsorption increasing with pH to a maximum at pH ∼6. We determine directly for the first time that Cu adsorbs to B. subtilis as a (CuO5Hn)n−8 monodentate, inner-sphere surface complex involving carboxyl surface functional groups. This Cu-carboxyl complex is able to account for the observed Cu adsorption across the entire pH range studied. Having determined the molecular adsorption mechanism of Cu to B. subtilis, we have developed a new thermodynamic surface complexation model for Cu adsorption that is informed by and consistent with EXAFS results. We model the surface electrostatics using the 1pK basic Stern approximation. We fit our adsorption data to the formation of a monodentate, inner-sphere RCOOCu+ surface complex. In agreement with previous studies, this work indicates that in order to accurately predict the fate and mobility of Cu in complex biogeochemical systems, we must incorporate the formation of Cu-bacteria surface complexes in reactive transport models. To this end, this work recommends log K RCOOCu+ = 7.13 for geologic and aqueous systems with generally high B. subtilis-to-metal ratio.  相似文献   

3.
Several recent studies have applied surface complexation theory to model metal adsorption behaviour onto mesophilic bacteria. However, no investigations have used this approach to characterise metal adsorption by thermophilic bacteria. In this study, we perform batch adsorption experiments to quantify cadmium adsorption onto the thermophile Anoxybacillus flavithermus. Surface complexation models (incorporating the Donnan electrostatic model) are developed to determine stability constants corresponding to specific adsorption reactions. Adsorption reactions and stoichiometries are constrained using spectroscopic techniques (XANES, EXAFS, and ATR-FTIR). The results indicate that the Cd adsorption behaviour of A. flavithermus is similar to that of other mesophilic bacteria. At high bacteria-to-Cd ratios, Cd adsorption occurs by formation of a 1:1 complex with deprotonated cell wall carboxyl functional groups. At lower bacteria-to-Cd ratios, a second adsorption mechanism occurs at pH > 7, which may correspond to the formation of a Cd-phosphoryl, CdOH-carboxyl, or CdOH-phosphoryl surface complex. X-ray absorption spectroscopic investigations confirm the formation of the 1:1 Cd-carboxyl surface complex, but due to the bacteria-to-Cd ratio used in these experiments, other complexation mechanism(s) could not be unequivocally resolved by the spectroscopic data.  相似文献   

4.
Copper isotopes may prove to be a useful tool for investigating bacteria-metal interactions recorded in natural waters, soils, and rocks. However, experimental data which attempt to constrain Cu isotope fractionation in biologic systems are limited and unclear. In this study, we utilized Cu isotopes (δ65Cu) to investigate Cu-bacteria interactions, including surface adsorption and intracellular incorporation. Experiments were conducted with individual representative species of Gram-positive (Bacillus subtilis) and Gram-negative (Escherichia coli) bacteria, as well as with wild-type consortia of microorganisms from several natural environments. Ph-dependent adsorption experiments were conducted with live and dead cells over the pH range 2.5-6. Surface adsorption experiments of Cu onto live bacterial cells resulted in apparent separation factors (Δ65Cusolution-solid = δ65Cusolution − δ65Cusolid) ranging from +0.3‰ to +1.4‰ for B. subtilis and +0.2‰ to +2.6‰ for E. coli. However, because heat-killed bacterial cells did not exhibit this behavior, the preference of the lighter Cu isotope by the cells is probably not related to reversible surface adsorption, but instead is a metabolically-driven phenomenon. Adsorption experiments with heat-killed cells yielded apparent separation factors ranging from +0.3‰ to −0.69‰ which likely reflects fractionation from complexation with organic acid surface functional group sites. For intracellular incorporation experiments the lab strains and natural consortia preferentially incorporated the lighter Cu isotope with an apparent Δ65Cusolution-solid ranging from ∼+1.0‰ to +4.4‰. Our results indicate that live bacterial cells preferentially sequester the lighter Cu isotope regardless of the experimental conditions. The fractionation mechanisms involved are likely related to active cellular transport and regulation, including the reduction of Cu(II) to Cu(I). Because similar intracellular Cu machinery is shared by fungi, plants, and higher organisms, the influence of biological processes on the δ65Cu of natural waters and soils is probably considerable.  相似文献   

5.
Apparent overall equilibrium constants for the adsorption of Cd, Cu, Ni, Pb and Zn onto natural iron oxyhydroxides have been calculated from the partitioning of these trace metals in oxic lake sediments and the in situ measurement of trace metal concentrations in the associated pore waters. Such values obtained from lakes of various pH located on the Precambrian Shield, in the area of Sudbury, Ontario, are compared with equilibrium constants obtained for the adsorption of the trace metals onto iron oxyhydroxides in well-defined media.The field data are consistent with laboratory experiments reported in the literature and with theory. Both the influence of pH upon adsorption and the binding strength sequence observed for the field data agree with theory. At high sediment pH values, the partitioning of Cd, Ni and Zn between the pore waters and the natural iron oxyhydroxides is similar to those reported in the literature for the adsorption of these metals at low surface coverage onto amorphous iron oxyhydroxides in a NaNO3 medium; deviation from this simple model is however observed for Cu and Pb, presumably due to the competitive action of dissolved ligands. At low sediment pH values, the adsorption is much higher than predicted by the simple model and can be explained by the formation of ternary complexes with the iron oxyhydroxide surface.  相似文献   

6.
The adsorption of Cu, Pb, Zn, and Cd on goethite (αFeOOH) from NaNO3 solutions and from major ion seawater was compared to assess the effect of the major ions of seawater (Na, Mg, Ca, K, Cl, and SO4) on the adsorption behavior of the metals. Magnesium and sulphate are the principal seawater ions which enhance or inhibit adsorption relative to the inert system. Their effect, as determined from the site-binding model of Davis et al. (1978), was a combination of changing the electrostatic conditions at the interface and decreasing the available binding sites.The basic differences between the experimental system of major ion seawater and natural seawater were examined. It was concluded that: 1) although the experimental metal concentrations in major ion seawater were higher than those found in natural seawater, estimates of the binding energy of Cu, Zn, and Cd with αFeOOH for natural seawater concentrations could be made from the data, 2) Cu, Pb, Zn, and Cd showed little or no competition for surface sites on goethite, and 3) the presence of carbonate, phosphate, and silicate had little or no effect on the adsorption of Zn and Cd on goethite.  相似文献   

7.
This work is devoted to the physico-chemical study of cadmium and lead interaction with diatom-water interfaces for two marine planktonic (Thalassiosira weissflogii, TW; Skeletonema costatum, SC) and two freshwater periphytic species (Achnanthidium minutissimum, AMIN; Navicula minima, NMIN) by combining adsorption measurements with surface complexation modeling. Adsorption kinetics was studied as a function of pH and initial metal concentration in sodium nitrate solution and in culture media. Kinetic data were consistent with a two-step mechanism in which the loss of a water molecule from the inner coordination sphere of the metal is rate limiting. Reversible adsorption experiments, with 3 h of exposure to metal, were performed as a function of pH (2-9), metal concentration in solution (10−9-10−3 M), and ionic strength (10−3-1.0 M). While the shape of pH-dependent adsorption edge is similar among all four diatom species, the constant-pH adsorption isotherm and maximal binding capacities differ. Measurements of electrophoretic mobilities (μ) revealed negative surface potential for AMIN diatom, however, the absolute value of μ decreases with increase of [Pb2+]aq suggesting the metal adsorption on negative surface sites. These observations allowed us to construct a surface complexation model (SCM) for cadmium and lead binding by diatom surfaces that postulates the Constant Capacitance of the electric double layer and considers Cd and Pb complexation with mainly carboxylic and, partially, silanol groups. In the full range of investigated Cd concentration, the SCM is able to describe the concentration of adsorbed metal as a function of [Cd2+]aq without implying the presence of high affinity, low abundance sites, that are typically used to model the metal interactions with natural multi-component organic substances. At the same time, Cd fast initial reaction requires the presence of “highly reactive sites” those concentration represents only 2.5-3% of the total amount of carboxylic sites. For reversible adsorption experiments, the dominating carboxylic groups, whose concentration is allowed to vary within the uncertainty of experimental acid-base titrations, are sufficient to reproduce the metal adsorption isotherms. Results of this study strongly suggest that laboratory experiments performed in a wide range of metal to biomass ratios, represent robust and relatively simple method for assessing the distribution of metals between aqueous solution and planktonic and periphytic biomass in natural settings.  相似文献   

8.
Adsorption of copper, cadmium and nickel at low concentrations on goethite was studied in the presence of the simple organic ligands oxalate, salicylate, and pyromellitate. The experimental metal adsorption behavior was compared to calculations with a surface complexation model to evaluate the most important interactions. Oxalate mostly decreased Cu and Ni adsorption at high pH-values by competition between solution and surface complexation but had no effect on Cd adsorption. Cu adsorption in the presence of oxalate below pH 6 could best be described by defining a ternary complex of type A (surface-metal-ligand). Salicylate had only minor effects on metal adsorption. The adsorption of Cu in the presence of salicylate above pH 5 could be explained by a ternary complex of type A. Pyromellitate increased the adsorption of Cu and Cd in the acidic pH-range, likely by formation of ternary surface complexes of type B (surface-ligand-metal).  相似文献   

9.
Bacterial surface adsorption can control metal distributions in some natural systems, yet it is unclear whether natural bacterial consortia differ in their adsorption behaviors. In this study, we conduct potentiometric titration and metal adsorption experiments to measure proton and Cd adsorption onto a range of bacterial consortia. We model the experimental data using a surface complexation approach to determine thermodynamic stability constants. Our results indicate that these consortia adsorb similar extents of protons and Cd and that the adsorption onto all of the consortia can be modeled using a single set of stability constants. Consortia of bacteria cultured from natural environments also adsorb metals to lesser extents than individual strains of laboratory-cultivated species. This study suggests that a wide range of bacterial species exhibit similar adsorption behaviors, potentially simplifying the task of modeling the distribution and speciation of metals in bacteria-bearing natural systems. Current models for bacteria-metal adsorption that rely on pure strains of laboratory-cultivated species likely overpredict the amount of bacteria-metal adsorption in natural systems.  相似文献   

10.
We used titration calorimetry to measure the bulk heats of proton and Cd adsorption onto a common Gram positive soil bacterium Bacillus subtilis at 25.0 °C. Using the 4-site non-electrostatic model of Fein et al. [Fein, J.B., Boily, J.-F., Yee, N., Gorman-Lewis, D., Turner, B.F., 2005. Potentiometric titrations of Bacillus subtilis cells to low pH and a comparison of modeling approaches. Geochim. Cosmochim. Acta69 (5), 1123-1132.] to describe the bacterial surface reactivity to protons, our bulk enthalpy measurements can be used to determine the following site-specific enthalpies of proton adsorption for Sites 1-4, respectively: −3.5 ± 0.2, −4.2 ± 0.2, −15.4 ± 0.9, and −35 ± 2 kJ/mol, and these values yield the following third law entropies of proton adsorption onto Sites 1-4, respectively: +51 ± 4, +78 ± 4, +79 ± 5, and +60 ± 20 J/mol K. An alternative data analysis using a 2-site Langmuir-Freundlich model to describe proton binding to the bacterial surface (Fein et al., 2005) resulted in the following site-specific enthalpies of proton adsorption for Sites 1 and 2, respectively: −3.6 ± 0.2 and −35.1 ± 0.3 kJ/mol. The thermodynamic values for Sites 1-3 for the non-electrostatic model and Site 1 of the Langmuir-Freundlich model of proton adsorption onto the bacterial surface are similar to those associated with multifunctional organic acid anions, such as citrate, suggesting that the protonation state of a bacterial surface site can influence the energetics of protonation of neighboring sites. Our bulk Cd enthalpy data, interpreted using the 2-site non-electrostatic Cd adsorption model of Borrok et al. [Borrok, D., Fein, J.B., Tischler, M., O’Loughlin, E., Meyer, H., Liss, M., Kemner, K.M., 2004b. The effect of acidic solutions and growth conditions on the adsorptive properties of bacterial surfaces. Chem. Geol.209 (1-2), 107-119.] to account for Cd adsorption onto B. subtilis, yield the following site-specific enthalpies of Cd adsorption onto bacterial surface Sites 2 and 3, respectively: −0.2 ± 0.4 and +14.4 ± 0.9 kJ/mol, and the following third law entropies of Cd adsorption onto Sites 2 and 3, respectively: +57 ± 4 and +128 ± 5 J/mol K. The calculated enthalpies of Cd adsorption are typical of those associated with Cd complexation with anionic oxygen ligands, and the entropies are indicative of inner sphere complexation by multiple ligands. The experimental approach described in this study not only yields constraints on the molecular-scale mechanisms involved in proton and Cd adsorption reactions, but also provides new thermodynamic data that enable quantitative estimates of the temperature dependence of proton and Cd adsorption reactions.  相似文献   

11.
高岭石对重金属离子的吸附机理及其溶液的pH条件   总被引：14，自引：0，他引：14  
高岭石对Cu^2+,Pb^2+离子的吸附实验及高岭石的溶解实验表明,高岭石对重金属离子的吸附有别于石英单一表面配位模式,离子交换和表面配位模式并存,并随溶液pH由酸性往碱性的变化发生规律性的演替：pH<6.5时主要表现为外圈层配位的离子交换吸附,且在pH<4时由于受到高岭石表层中铝的高溶出及溶液中较高离子强度的影响,高岭石对Cu^2+,Pb^2+离子的吸附率较低,pH为5～6时由于高岭石端面的荷电性为近中性,吸附率则有明显的提升并且表现为一个吸附平台;pH>6.5时离子交换和表面配位均为重要吸附机制,pH再升高时沉淀机制则起着重要作用。研究表明,pH调控高岭石-水界面溶解与质子化-去质子化反应过程,并影响着Cu^2+,Pb^2+离子的吸附行为。最后采用Sverjensky(1993)表面配位的物理模型对吸附结果作了描述。  相似文献   

12.
This work aimed to investigate the adsorption characteristics, both kinetically and thermodynamically, of Cu(II) and Pb(II) removal from aqueous solutions onto mixed-waste activated carbon, as well as to study the competitive behavior found in mixed heavy metal solution systems. This study shows that activated carbon prepared from mixed waste is an effective adsorbent for the removal of Cu(II) and Pb(II) from aqueous solutions, with the aim of detoxifying industrial effluents before their safe disposal onto water surfaces. The adsorption process was characterized in terms of kinetic and thermodynamic studies. In addition, the influence of presence of Cu(II) and Pb(II) in a competitive system was investigated. The results showed that the maximum adsorption capacities were gained at a pH of 6 with a contact time of 180 min, a metal solution concentration of 300 ppm, and an adsorbent dose of 0.3 g/L. The adsorption process was found to follow a pseudo-first-order kinetic model. Thermodynamic parameters such as ΔG o, ΔH o, and ΔS o showed that the sorption process was spontaneous and endothermic in nature. A competitive study demonstrated the applicability of mixed-waste activated carbon to adsorb Cu(II) and Pb(II) from a solution of mixed metals. In addition, the adsorption capacity was found to be as effective as other adsorbents reported in the literature. The developed adsorptive removal procedure was applied for treatment of real wastewater samples and showed high removal efficiency.  相似文献   

13.
The bioavailability and fate of heavy metals in the environment are often controlled by sorption reactions on the reactive surfaces of soil minerals. We have developed a non-electrostatic equilibrium model (NEM) with both surface complexation and ion exchange reactions to describe the sorption of Pb and Cd in single- and binary-metal systems over a range of pH and metal concentration. Mineralogical and exchange properties of three different acidic soils were used to constrain surface reactions in the model and to estimate surface densities for sorption sites, rather than treating them as adjustable parameters. Soil heterogeneity was modeled with >FeOH and >SOH functional groups, representing Fe- and Al-oxyhydroxide minerals and phyllosilicate clay mineral edge sites, and two ion exchange sites (X− and Y−), representing clay mineral exchange. An optimization process was carried out using the entire experimental sorption data set to determine the binding constants for Pb and Cd surface complexation and ion exchange reactions.Modeling results showed that the adsorption of Pb and Cd was distributed between ion exchange sites at low pH values and specific adsorption sites at higher pH values, mainly associated with >FeOH sites. Modeling results confirmed the greater tendency of Cd to be retained on exchange sites compared to Pb, which had a higher affinity than Cd for specific adsorption on >FeOH sites. Lead retention on >FeOH occurred at lower pH than for Cd, suggesting that Pb sorbs to surface hydroxyl groups at pH values at which Cd interacts only with exchange sites. The results from the binary system (both Pb and Cd present) showed that Cd retained in >FeOH sites decreased significantly in the presence of Pb, while the occupancy of Pb in these sites did not change in the presence of Cd. As a consequence of this competition, Cd was shifted to ion exchange sites, where it competes with Pb and possibly Ca (from the background electrolyte). Sorption on >SOH functional groups increased with increasing pH but was small compared to >FeOH sites, with little difference between single- and binary-metal systems. Model reactions and conditional sorption constants for Pb and Cd sorption were tested on a fourth soil that was not used for model optimization. The same reactions and constants were used successfully without adjustment by estimating surface site concentrations from soil mineralogy. The model formulation developed in this study is applicable to acidic mineral soils with low organic matter content. Extension of the model to soils of different composition may require selection of surface reactions that account for differences in clay and oxide mineral composition and organic matter content.  相似文献   

14.
《Applied Geochemistry》2001,16(5):503-511
The use of adsorption data from single sorbate systems to model metal adsorption in SO4-rich waters, such as acid mine drainage, can lead to inaccurate predictions of metal speciation. The adsorption of Cu and Zn on ferrihydrite, for example, is enhanced at low pH values in the presence of SO4. This effect can only be accurately modeled using the diffuse layer model and surface complexation theory if ternary surface complexes, ≡FeOHCuSO4 or ≡FeOHZnSO4, are taken into consideration. Intrinsic adsorption constants for the formation of these ternary complexes on ferrihydrite have been derived from experimental data. When included in the model, Cu and Zn adsorption in the presence of SO4 is accurately predicted for a wide range of metal, ferrihydrite and SO4 concentrations. Adsorption of Cu and Zn onto the SO4-rich Fe oxyhydroxide, schwertmannite, could also be accurately predicted and is indistinguishable from adsorption onto ferrihydrite in the presence of high solution SO4 concentrations (e.g. 0.01 mol kg−1 SO4).  相似文献   

15.
Rare earth element (REE) adsorption onto sand from a well characterized aquifer, the Carrizo Sand aquifer of Texas, has been investigated in the laboratory using a batch method. The aim was to improve our understanding of REE adsorption behavior across the REE series and to develop a surface complexation model for the REEs, which can be applied to real aquifer-groundwater systems. Our batch experiments show that REE adsorption onto Carrizo sand increases with increasing atomic number across the REE series. For each REE, adsorption increases with increasing pH, such that when pH >6.0, >98% of each REE is adsorbed onto Carrizo sand for all experimental solutions, including when actual groundwaters from the Carrizo Sand aquifer are used in the experiments. Rare earth element adsorption was not sensitive to ionic strength and total initial REE concentrations in our batch experiments. It is possible that the differences in experimental ionic strength conditions (i.e., 0.002-0.01 M NaCl) chosen were insufficient to affect REE adsorption behavior. However, cation competition (e.g., Ca, Mg, and Zn) did affect REE adsorption onto Carrizo sand, especially for light rare earth elements (LREEs) at low pH. Rare earth element adsorption onto Carrizo sand can be successfully modeled using a generalized two-layer surface complexation model. Our model calculations suggest that REE complexation with strong surface sites of Carrizo sand exceeds the stability of the aqueous complexes LnOH2+, LnSO4+, and LnCO3+, but not that of Ln(CO3)2- or LnPO4o in Carrizo groundwaters. Thus, at low pH (<7.3), where major inorganic ligands did not effectively compete with surface sites for dissolved REEs, free metal ion (Ln3+) adsorption was sufficient to describe REE adsorption behavior. However, at higher pH (>7.3) where solution complexation of the dissolved REEs was strong, REEs were adsorbed not only as free metal ion (Ln3+) but also as aqueous complexes (e.g., as Ln(CO3)2- in Carrizo groundwaters). Because heavy rare earth elements (HREEs) were preferentially adsorbed onto Carrizo sand compared to LREEs, original HREE-enriched fractionation patterns in Carrizo groundwaters from the recharge area flattened along the groundwater flow path in the Carrizo Sand aquifer due to adsorption of free- and solution-complexed REEs.  相似文献   

16.
Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (KFe–M) and anionic (KFe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of KFe–M and KFe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (KPOM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of KPOM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.  相似文献   

17.
《Geochimica et cosmochimica acta》1999,63(19-20):2929-2938
The competitive sorption of Cu(II) and Pb(II) to colloidal hematite was investigated as a function of pH and total metal concentration. Acid–base titrations of the hematite and single-metal sorption experiments for Cu and Pb at low to medium surface coverages were used to calibrate two surface complexation models, the triple layer model, and a 2-pK basic Stern model with ion-pair formation. The surface site density was systematically varied from 2 to 20 sites/nm2. Three different metal surface complexes were considered: (1) an inner-sphere metal complex; (2) an outer-sphere metal complex; and (3) an outer-sphere complex of singly hydrolyzed metal cations. Both models provided excellent fits to acid–base titration and single-metal sorption data, regardless of the surface site density used. With increasing site density, ΔpK of the stability constants for protonation reactions increased and metal surface complexes decreased steadily. The calibrated models based on different site densities were used to predict competitive sorption effects between Cu and Pb and single-metal sorption at higher total metal concentrations. Precipitation of oversaturated solid phases was included in the calculations. Best predictions of competitive sorption effects were obtained with surface site densities between 5 and 10 sites/nm2. The results demonstrate that surface site density is a key parameter if surface complexation models are exposed to more complex, multicomponent environments. We conclude that competitive metal sorption experiments can be used to obtain additional information about the relevant surface site density of oxide mineral surfaces.  相似文献   

18.
The adsorption of five toxic metallic cations, Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II), onto montmorillonite was investigated as a function of pH and ionic strength and a two-site surface complexation model was used to predict the adsorption data. The results showed that in the lower pH range, 3∼6 for Cd, Cu, Ni and Zn, and 3∼4.5 for Pb, the adsorption was greatly affected by ionic strength, while in the higher pH range, the adsorption was not. In the lower pH range, the metallic cations were mainly bound through the formation of outer-sphere surface on the permanently charged basal surface sites (≡X−), while in the higher pH range the adsorption occurred mainly on the variably charged edge sites (≡SOH) through the formation of inner-sphere surface complexes. Acid-base surface constants and metal binding constants for the two sites were optimized using FITEQL. The adsorption affinity of the five metallic cations to the permanently charged sites of montmorillonite was Pb > Cu > Ni ≈ Zn ≈ Cd, while that to the variable charged sites was Pb ? Cu > Zn > Cd > Ni.  相似文献   

19.
《Applied Geochemistry》2006,21(7):1135-1151
Trace metal adsorption to suspended particulate matter (SPM) influences bioavailability and toxicity of trace metals in natural waters. For highly contaminated urban catchments in the greater Auckland (New Zealand) area, trace metal adsorption to SPM was assessed and compared to similar data from non-urban catchments in the Auckland region, to determine whether there was any difference in the ability of the SPM to adsorb Cu, Pb and Zn. The degree of trace metal adsorption onto the SPM was assessed by way of adsorption edge experiments. It was found that the ability of the Auckland urban SPM to adsorb trace metals decreased in the order Pb > Cu > Zn. Little difference in adsorption was observed between the non-urban Waikato and Kaipara River SPM and urban SPM, or between urban SPM from different flow regimes and seasons, despite some compositional differences in the SPM. This suggests that on the basis of a single surface-binding site, metal adsorption onto SPM could be readily predicted across a range of urban and non-urban catchments in the Auckland region. Adsorption edges were modelled with a diffuse layer, surface complexation model to assess the role of Fe-oxide in adsorption. The MINTEQA2 model was used, assuming Fe-oxide (as HFO) was the only adsorbing surface. There was generally good agreement between observed and modelled adsorption for Pb, indicating the importance of Fe-oxide surfaces for Pb adsorption. However, the model did not predict Zn or Cu adsorption as well. The TOC content of the SPM, and presence of dissolved ligands and organic matter in the water column, appeared to play an important role in Cu adsorption to the SPM. For Zn, the presence of adsorbing surfaces other than HFO appeared to influence adsorption.  相似文献   

20.
《Applied Geochemistry》2001,16(9-10):1067-1082
Thermodynamic data for all fate-determining processes are needed in order to predict the fate and transport of metals in natural systems. The surface complexation properties of a synthetic MnO2, δ-MnO2, have accordingly been investigated using glass electrode potentiometry. Experimental data were interpreted according to the surface complexation model in conjunction with the diffuse double layer model of the solid/solution interface. Adsorption constants were determined using the non-linear optimisation program FITEQL. Surface complexation parameters determined in this way were validated against results obtained from the literature. Best fits of alkalimetric titration data were obtained with a 2-site, 3 surface-species model of the δ-MnO2 surface. Site concentrations of 2.23×10−3 mol g−1 and 7.66×10−4 mol g−1 were obtained. Corresponding logarithms of formation constants for the postulated surface species are −1.27 (≡XO−), −5.99 (≡YO−) and 3.52 (≡YOH2+) at I=0.1 M. The surface speciation of δ-MnO2 is dominated by ≡XO− over the pH range investigated. Metal adsorption was modelled with surface species of the type ≡XOM+, ≡XOMOH, ≡YOM+, ≡YOMOH (M=Cu, Ni, Zn, Cd and Pb) and ≡XOM2OH2+ (M=Pb). For Cu, Ni and Zn, titration data could be modelled with ≡XOM+, ≡XOMOH, ≡YOM+ and ≡YOMOH, whereas for Cd, ≡XOM+ and ≡YOM+ were sufficient. Lead data were best modelled by assuming the dinuclear species ≡XOM2OH2+ to be the only surface species to form. Adsorption constants determined for Ni, Cu and Zn follow the Irving-Williams sequence. The model suggests an adsorption order of (Pb, Cu) > (Ni, Zn) > Cd. The discrepancy between model predictions and published adsorption results is similar to the variability observed in experimental results from different laboratories.  相似文献   

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