共查询到20条相似文献，搜索用时 46 毫秒
1.
2.
《Geochimica et cosmochimica acta》1999,63(19-20):3059-3067
In order to test the ability of a surface complexation approach to account for metal-bacteria interactions in near surface fluid-rock systems, we have conducted experiments that measure the extent of adsorption in mixed metal, mixed bacteria systems. This study tests the surface complexation approach by comparing estimated extents of adsorption based on surface complexation modeling to those we observed in the experimental systems. The batch adsorption experiments involved Ca, Cd, Cu, and Pb adsorption onto the surfaces of 2 g positive bacteria: Bacillus subtilis and Bacillus licheniformis. Three types of experiments were performed: 1. Single metal (Ca, Cu, Pb) adsorption onto a mixture of B. licheniformis and B. subtilis; 2. mixed metal (Cd, Cu, and Pb; Ca and Cd) adsorption onto either B. subtilis or B. licheniformis; and 3. mixed or single metal adsorption onto B. subtilis and B. licheniformis. %Independent of the experimental results, and based on the site specific stability constants for Ca, Cd, Cu, and Pb interactions with the carboxyl and phosphate sites on B. licheniformis and B. subtilis determined by Fein et al. (1997), by Daughney et al. (1998) and in this study, we estimate the extent of adsorption that is expected in the above experimental systems.Competitive cation adsorption experiments in both single and double bacteria systems exhibit little adsorption at pH values less than 4. With increasing pH above 4.0, the extent of Ca, Cu, Pb and Cd adsorption also increases due to the increased deprotonation of bacterial surface functional groups. In all cases studied, the estimated adsorption behavior is in excellent agreement with the observations, with only slight differences that were within the uncertainties of the estimation and experimental procedures. Therefore, the results indicate that the use of chemical equilibrium modeling of aqueous metal adsorption onto bacterial surfaces yields accurate predictions of the distribution of metals in complex multicomponent systems. 相似文献
3.
Competitive sorption and desorption of cadmium and lead in paddy soils of eastern China 总被引：3，自引：0，他引：3
To assess the competitive sorption and desorption of cadmium (Cd) and lead (Pb), batch equilibrium experiments were performed using single- and binary-metal solutions in surface samples of three paddy soils from eastern China. Sorption isotherms were well fitted with one-metal and competitive Langmuir equation for single- and binary-metal system, respectively. The distribution coefficient (K d) values were K d single (Pb) > K d binary (Pb) > K d single (Cd) > K d binary (Cd), indicating that Pb was stronger sorbed by these soils than Cd in binary metal system. Soils with high pH and clay content had the greatest sorption capacity as estimated by the maximum sorption parameter (Q). The co-existence of both metals reduces their tendency of sorption, whereas Cd sorption was affected to a greater extent than that of Pb. The Langmuir binding strength parameter (b) in binary sorption system was greater than that in single sorption system for all soils (b < b 1), indicating that competition for sorption sites promote the retention of both metals into more specific sorption sites. Sorption of Cd and Pb decreased soil pH by 1.61 U for YRS, 1.39 U for PCS, and 0.91 U for SLS. The decreases of pH in binary metal system were greater than in single-metal system for three soils. Cadmium and Pb desorption increased with increasing Cd and Pb sorption saturation for all soils; however, Cd desorption ratio in binary metal system (d Cd*) was much greater than Pb (d Pb*), indicating that under the competitive sorption conditions, the sorbed Cd was more readily desorbed from the soils than the sorbed Pb. 相似文献
4.
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
5.
The ability to predict the fate and transport of arsenic in aquatic environments, its impact on water quality and human health, and the performance and cost-effectiveness of water treatment systems relies on understanding how it interacts with solid surfaces. In situ resonant surface X-ray scattering measurements of arsenate adsorption at pH 5 in 0.01 M NaCl on corundum and hematite (012) surfaces demonstrate that arsenate surface complexation is unexpectedly bimodal, adsorbing simultaneously as inner- and outer-sphere species. In addition, this bimodal behavior is found to be independent of the total arsenate solution concentration, and thus surface coverage, over the range of 10−6 to 10−3 M. Alternative mechanisms to produce the observed As distributions, such as arsenate dimerization or surface precipitation of an aluminum or ferric arsenate, are inconsistent with the experimentally-determined total and As-specific density profiles. Based on the location of the outer-sphere arsenate in relation to the surfaces studied, possible binding mechanisms include electrostatic attraction, hydrogen bonding to surface oxygen functional group, and configurational stabilization by interfacial water. Although the observation of outer-sphere arsenate surface complexes on a metal oxide surface is unprecedented, it is unclear if such species were absent in previous molecular-scale studies, as it is difficult for methods commonly used to investigate the mechanisms of arsenate adsorption to conclusively identify or rule out the presence of outer-sphere species when inner-sphere species are also present. 相似文献
6.
In this study, we conducted electrophoretic mobility, potentiometric titration, and metal sorption experiments to investigate the surface charge characteristics of Bacillus subtilis and the electrostatic interactions between metal cations and the cell surface electric field. Electrophoretic mobility experiments performed as a function of pH and ionic strength show an isoelectric point of pH 2.4, with the magnitude of the electrokinetic potential increasing with increasing pH, and decreasing with increasing ionic strength. Potentiometric titration experiments conducted from pH 2.4 to 9 yield an average surface charge excess of 1.6 μmol/mg (dry mass). Corresponding cell wall charge density values were used to calculate the Donnan potential (ΨDON) as function of pH and ionic strength. Metal sorption experiments conducted with Ca(II), Sr(II), and Ba(II) exhibit strong ionic strength dependence, suggesting that the metal ions are bound to the bacterial cell wall via an outer-sphere complexation mechanism. Intrinsic metal sorption constants for the sorption reactions were determined by correcting the apparent sorption constant with the Boltzmann factor. A 1:2 metal-ligand stoichiometry provides the best fit to the experimental data with log K2int values of 5.9 ± 0.3, 6.0 ± 0.2, 6.2 ± 0.2 for Ca(II), Sr(II), and Ba(II) respectively. Electrophoretic mobility measurements of cells sorbed with Ca(II), Sr(II), and Ba(II) support the 1:2 sorption stoichiometry. These results indicate that electrical potential parameters derived from the Donnan model can be applied to predict metal binding onto bacterial surfaces over a wide range of pH and ionic strength conditions. 相似文献
7.
Susana Serrano Peggy A. O’Day Maria Teresa García-González 《Geochimica et cosmochimica acta》2009,73(3):543-558
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
8.
《Applied Geochemistry》2003,18(4):527-538
Thermodynamic parameters for proton and metal adsorption onto a gram-negative bacterium from the genus Enterobacteriaceae have been determined and compared with parameters for other strains of bacteria. Potentiometric titrations were used to determine the different types of sites present on bacterial cell walls. Stability constants for adsorption of Pb, Cu and Zn to specific sites were determined from batch adsorption experiments at varying pH with constant metal concentration. Titrations revealed 3 distinct acidic surface sites on the bacterial surface, with pK values of 4.3±0.2, 6.9±0.5 and 8.9±0.5, corresponding to carboxyl, phosphate and hydroxyl/amine groups, with surface densities of 5.0±0.7×10−4, 2.2±0.6×10−4 and 5.5±2.2×10−4 mol/g of dry bacteria. Only carboxyl and phosphate sites are involved in metal uptake, yielding the following intrinsic stability constants: Log Kcarboxyl: Zn=3.3±0.1, Pb=3.9±0.8, and Cu=4.4±0.2, Log Kphosphoryl: Zn=5.1±0.1 and Pb=5.0±0.9. The deprotonation constants are similar to those of other strains of bacteria, while site densities are also within an order of magnitude of other strains. The similarities in surface chemistry and metal stability constants suggest that bacteria may be represented by a simple generic thermodynamic model for the purposes of modelling metal transport in natural environments. Comparison with oxide-coated sand shows that bacteria can attenuate some metals to much lower pH values. 相似文献
9.
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
10.
Sorption of the 14 rare earth elements (REE) by basaltic rock is investigated as a function of pH, ionic strength and aqueous REE concentrations. The rock sample, originating from a terrestrial basalt flow (Rio Grande do Sul State, Brazil), is composed of plagioclase, pyroxene and cryptocrystalline phases. Small amounts of clay minerals are present, due to rock weathering. Batch sorption experiments are carried out under controlled temperature conditions of 20 °C with the <125 μm fraction of the ground rock in solutions of 0.025 M and 0.5 M NaCl and at pH ranging from 2.7 to 8. All 14 REEs are investigated simultaneously with initial concentrations varying from 10−7 to 10−4 mol/L. Some experiments are repeated with only europium present to evaluate possible competitive effects between REE. Experimental results show the preferential retention of the heavy REEs at high ionic strength and circumneutral pH conditions. Moreover, results show that REE sorption increases strongly with decreasing ionic strength, indicating two types of sorption sites: exchange and specific sites. Sorption data are described by a Generalised Composite (GC) non-electrostatic model: two kinds of surface reactions are treated, i.e. cation exchange at >XNa sites, and surface complexation at >SOH sites. Total site density (>XNa + >SOH) is determined by measuring the cation exchange capacity (CEC = 52 μmol/m2). Specific concentrations of exchange sites and complexation sites are determined by fitting the Langmuir equation to sorption isotherms of REE and phosphate ions. Site densities of 22 ± 5 and 30 ± 5 μmol/m2 are obtained for [>XNa] and [>SOH], respectively. The entire set of REE experimental data is modeled using a single exchange constant (log Kex = 9.7) and a surface complexation constant that progressively increases from log K = −1.15 for La(III) to −0.4 for Lu(III).The model proves to be fairly robust in describing other aluminosilicate systems. Maintaining the same set of sorption constants and only adjusting the site densities, we obtain good agreement with the literature data on REE/kaolinite and REE/smectite sorption. The Generalised Composite non-electrostatic model appears as an easy and efficient tool for describing sorption by complex aluminosilicate mineral assemblages. 相似文献
11.
《Geochimica et cosmochimica acta》1999,63(19-20):2957-2969
Fourier transform infrared (FTIR) and extended X-ray absorption fine structure (EXAPS) spectroscopic measurements were performed on Pb(II)ethylenediaminetetraacetic (EDTA) adsorbed on goethite as a function of pH (4–6), Pb(II)EDTA concentration (0.11–72 μM), and ionic strength (16 μM–0.5 M). FTIR measurements show no evidence for carboxylate-Fe(III) bonding or protonation of EDTA at Pb:EDTA = 1:1. Both FTIR and EXAFS spectroscopic measurements suggest that EDTA acts as a hexadentate ligand, with all four of its carboxylate and both of its amine groups bonded to Pb(II). No evidence was observed for inner-sphere Pb(II)-goethite bonding at Pb:EDTA = 1:1. Hence, the adsorbed complexes should have composition Pb(II)EDTA2−. Because substantial uptake of PbEDTA(II)2− occurred in the samples, we interpret that Pb(II)EDTA2− adsorbed as outer-sphere complexes and/or as complexes that lose part of their solvation shells and hydrogen bond directly to goethite surface sites. We propose the term “hydration-sphere” for the latter type of complexes because they should occupy space in the primary hydration spheres of goethite surface functional groups and to distinguish this mode of sorption from common structural definitions of inner- and outer-sphere complexes. The lack of evidence for inner-sphere EDTA-Fe(III) bonding suggests that previously proposed metal/ligand-promoted dissolution mechanisms should be modified, specifically to account for the presence of outer-sphere precursor species. 相似文献
12.
Experimental studies of the reactions of Cu(II), Pb(II), and Zn(II) in aqueous solutions with organic matter derived from fresh samples of the green filamentous algae Ulothrix spp. and the green unicellular algae Chlamydomonas spp. and Chlorella vulgaris show that, under suitable conditions, a significant proportion of the metals is removed from solution by sorption onto the particulate organic matter of the algal suspension.The metal sorption is strongly suppressed by H+ but is only marginally influenced by the proportion of whole cells in the suspension and by complexing of metals in solution by the soluble organic matter. The presence of relatively small amounts of the cations Na+ and Mg2+ in solution reduces the sorption of Zn(II) to near zero, but Pb(II) and Cu(II) sorption occurs to an appreciable extent even in strong brines. This may be a means for the selective precipitation of Pb(II) from brines rich in Pb(II) and Zn(II).Metal “saturation” values indicate that particulate algal matter of the type used in these experiments could sorb sufficient quantities of metal to form an ore deposit if a weight of organic matter of similar order of magnitude to that of the inorganic sediments in the deposits was available. However, the metal sorption is an equilibrium reaction, and the experimentally determined “enrichment factors” suggest that the “saturation” values could be approached only in solutions whose metal contents were initially at least two orders of magnitude above those of normal seawater. 相似文献
13.
Sorption of Cu and Pb to kaolinite-fulvic acid colloids: Assessment of sorbent interactions 总被引：2，自引：0，他引：2
Ilona Heidmann 《Geochimica et cosmochimica acta》2005,69(7):1675-1686
The sorption of Cu(II) and Pb(II) to kaolinite-fulvic acid colloids was investigated by potentiometric titrations. To assess the possible interactions between kaolinite and fulvic acid during metal sorption, experimental sorption isotherms were compared with predictions based on a linear additivity model (LAM). Suspensions of 5 g L−1 kaolinite and 0.03 g L−1 fulvic acid in 0.01 M NaNO3 were titrated with Cu and Pb solutions, respectively. The suspension pH was kept constant at pH 4, 6, or 8. The free ion activities of Cu2+ and Pb2+ were monitored in the titration vessel using ion selective electrodes. Total dissolved concentrations of metals (by ICP-MS) and fulvic acid (by UV-absorption) were determined in samples taken after each titration step. The amounts of metals sorbed to the solid phase, comprised of kaolinite plus surface-bound fulvic acid, were calculated by difference. Compared to pure kaolinite, addition of fulvic acid to the clay strongly increased metal sorption to the solid phase. This effect was more pronounced at pH 4 and 6 than at pH 8, because more fulvic acid was sorbed to the kaolinite surface under acidic conditions. Addition of Pb enhanced the sorption of fulvic acid onto kaolinite at pH 6 and 8, but not at pH 4. Addition of Cu had no effect on the sorption of fulvic acid onto kaolinite. In the LAM, metal sorption to the kaolinite surface was predicted by a two-site, 1-pK basic Stern model and metal sorption to the fulvic acid was calculated with the NICA-Donnan model, respectively. The LAM provided good predictions of Cu sorption to the kaolinite-fulvic acid colloids over the entire range in pH and free Cu2+ ion activity (10−12 to 10−5). The sorption of Pb was slightly underestimated by the LAM under most conditions. A fractionation of the fulvic acid during sorption to kaolinite was observed, but this could not explain the observed deviations of the LAM predictions from the experimental Pb sorption isotherms. 相似文献
14.
15.
Mariëtte Wolthers Laurent Charlet Peter R. van der Linde 《Geochimica et cosmochimica acta》2005,69(14):3483-3492
Arsenate, As(V), sorption onto synthetic iron(II) monosulfide, disordered mackinawite (FeS), is fast. As(V) sorption decreases above the point of zero surface charge of FeS and follows the pH-dependent concentration of positively charged surface species. No redox reaction is observed between the As(V) ions and the mineral surface over the time span of the experiments. This observation shows that As(V) dominantly forms an outer-sphere complex at the surface of mackinawite. Arsenite, As(III), sorption is not strongly pH-dependent and can be expressed by a Freundlich isotherm. Sorption is fast, although slower than that of As(V). As(III) also forms an outer-sphere complex at the surface of mackinawite. In agreement with previous spectroscopic studies, complexation at low As(V) and As(III) concentration occurs preferentially at the mono-coordinated sulfide edge sites. The Kd (L g−1) values obtained from linear fits to the isotherm data are ∼9 for As(V) and ∼2 for As(III). Stronger sorption of As(V) than As(III), and thus a higher As(III) mobility, may be reflected in natural anoxic sulfidic waters when disordered mackinawite controls arsenic mobility. 相似文献
16.
A multisite surface complexation (MUSIC) model for ferrihydrite (Fh) has been developed. The surface structure and composition of Fh nanoparticles are described in relation to ion binding and surface charge development. The site densities of the various reactive surface groups, the molar mass, the mass density, the specific surface area, and the particle size are quantified. As derived theoretically, molecular mass and mass density of nanoparticles will depend on the types of surface groups and the corresponding site densities and will vary with particle size and surface area because of a relatively large contribution of the surface groups in comparison to the mineral core of nanoparticles. The nano-sized (∼2.6 nm) particles of freshly prepared 2-line Fh as a whole have an increased molar mass of M ∼ 101 ± 2 g/mol Fe, a reduced mass density of ∼3.5 ± 0.1 g/cm3, both relatively to the mineral core. The specific surface area is ∼650 m2/g. Six-line Fh (5-6 nm) has a molar mass of M ∼ 94 ± 2 g/mol, a mass density of ∼3.9 ± 0.1 g/cm3, and a surface area of ∼280 ± 30 m2/g. Data analysis shows that the mineral core of Fh has an average chemical composition very close to FeOOH with M ∼ 89 g/mol. The mineral core has a mass density around ∼4.15 ± 0.1 g/cm3, which is between that of feroxyhyte, goethite, and lepidocrocite. These results can be used to constrain structural models for Fh. Singly-coordinated surface groups dominate the surface of ferrihydrite (∼6.0 ± 0.5 nm−2). These groups can be present in two structural configurations. In pairs, the groups either form the edge of a single Fe-octahedron (∼2.5 nm−2) or are present at a single corner (∼3.5 nm−2) of two adjacent Fe octahedra. These configurations can form bidentate surface complexes by edge- and double-corner sharing, respectively, and may therefore respond differently to the binding of ions such as uranyl, carbonate, arsenite, phosphate, and others. The relatively low PZC of ferrihydrite can be rationalized based on the estimated proton affinity constant for singly-coordinated surface groups. Nanoparticles have an enhanced surface charge. The charging behavior of Fh nanoparticles can be described satisfactory using the capacitance of a spherical Stern layer condenser in combination with a diffuse double layer for flat plates. 相似文献
17.
M.H. Bradbury 《Geochimica et cosmochimica acta》2009,73(4):1004-5168
Sorption edge data for Ni(II), Co(II), Eu(III) and Sn(IV) [Bradbury M. H. and Baeyens B. (2009) Sorption modelling on illite. Part I: titration measurements and sorption of Ni(II), Co(II), Eu(III) and Sn(IV), Part I] on purified Na-Illite du Puy are available from some previous work, and some new measurements for Am(III), Th(IV), Pa(V) and U(VI) are presented here. All of these sorption edge measurements have been modelled with a 2 site protolysis non-electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model for which the site types, site capacities and protolysis constants were fixed [Bradbury M. H. and Baeyens B. (2009), Part I]. In addition, two further data sets for the sorption of Am(III) and Np(V) on Illite du Puy, obtained from the literature, were also modelled in this work. Thus, surface complexation constants for the strong sites in the 2SPNE SC/CE sorption model for nine metals with valence states from II to VI have been obtained. A linear relationship between the logarithm of strong site metal binding constants, SKx−1, and the logarithm of the corresponding aqueous hydrolysis stability constant, OHKx, extending over nearly 35 orders of magnitude is established here for illite for these nine metals. Such correlations are often termed linear free energy relationships (LFER), and although they are quite common in aqueous phase chemistry, they are much less so in surface chemistry, especially over this large range. The LFER for illite could be described by the equation: where, “x” is an integer. A similar relationship has been previously obtained for montmorillonite, thus LFERs relating to the sorption on two of the most important clay minerals present in natural systems have been established. Such an LFER approach is an extremely useful tool for estimating surface complexation constants for metals in a chemically consistent manner. It provides a means of obtaining sorption values for radionuclides for which there are no measured values and thus allows gaps in missing sorption data to be filled. An ultimate goal of this approach is to develop a thermodynamic sorption database. This could then be used in radioactive waste management performance assessment studies to calculate sorption in natural systems, and thereby replace the current usage of single solid liquid distribution coefficients (Kd values) to describe radionuclide uptake. Finally, with the data now available, the 2SPNE SC/CE sorption model can be ported into reactive transport models allowing radionuclide migration to be calculated under spatially and temporally changing conditions. 相似文献
18.
In solution thermodynamics, and more recently in surface chemistry, it is well established that relationships can be found between the free energies of formation of aqueous or surface metal complexes and thermodynamic properties of the metal ions or ligands. Such systematic dependencies are commonly termed linear free energy relationships (LFER). A 2 site protolysis non-electrostatic surface complexation and cation exchange (2SPNE SC/CE) model has been used to model “in house” and literature sorption edge data for eleven elements: Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Eu(III), Am(III), Sn(IV), Th(IV), Np(V) and U(VI) to provide surface complexation constants for the strong sites on montmorillonite. Modelling a further 4 sets of sorption isotherms for Ni(II), Zn(II), Eu(III) and U(VI) provided complexation constants for the weak sites. The protolysis constants and site capacities derived for the 2SPNE SC/CE model in previous work were fixed in all of the calculations. Cation exchange was modelled simultaneously to provide selectivity coefficients. Good correlations between the logarithms of strong SKx−1 and weak W1Kx−1 site binding constants on montmorillonite and the logarithm of the aqueous hydrolysis constants OHKx were found which could be described by the following equations: Strong (≡SSOH) sites:
SlogKX−1=8.1±0.3+(0.90±0.02)logOHKX 相似文献
19.
Total concentrations of and binding capacities for Cd, Cu, and Pb were measured in selected surface waters from northwestern Europe. Linear multiple regression predictive models explained 97, 93, and 96% of the observed variation in Cd, Cu and Pb binding capacities, respectively. The models constructed used (CO23?) and (SO22?) to predict Cd binding capacity, (OH?) and (SO42?) to predict Cu binding capacity and (OH?), (CO32?) and (SO42?) to predict Pb binding capacity. Organic carbon was not significantly correlated with binding capacities for Cd, Cu, and Pb and was unimportant in explaining a significant amount of the variability in binding capacities for the metals of northern European surface waters. Thus, the effects of these organics on trace metal speciation can be ignored and predictive models of trace metal speciation constructed, using inorganic solubility equilibria only. Ratios of total Cd, Cu, and Pb concentrations to their respective binding capacities were much less than unity for all waters studied. Copper exhibited the greatest metal concentrations: binding capacity ratio in all waters investigated. 相似文献
20.
Hexagonal birnessite (δ-MnO2) is a close analogue to the dominant phase in hydrogenetic marine ferromanganese crusts and nodules. These deposits contain ∼0.25 wt.% Cu which is believed to be scavenged from the overlying water column where Cu concentrations are near 0.1 μg/L. Here, we measured the sorption of Cu on δ-MnO2 as a function of pH and surface loading. We characterized the nature of the Cu sorption complex at pH 4 and 8 using EXAFS spectroscopy and find that, at pH 4, Cu sorbs to birnessite by inner-sphere complexation on the {0 0 1} surface at sites above Mn vacancies to give a three to fourfold coordinated complex with 6 Mn neighbors at ∼3.4 Å. At pH 8, however, we find that some Cu has become structurally incorporated into the MnO2 layer by occupying the vacancy sites to give 6 Mn neighbors at ∼2.91 Å. Density functional calculations on and clusters predict a threefold coordinated surface complex and show that the change from surface complexation to structural incorporation is a response to protonation of oxygens surrounding the vacancy site. Consequently, we propose that the transformation between sorption via surface complex and vacancy site occupancy should be reversible. By fitting the Cu sorption as a function of surface loading and pH to the formation of the observed and predicted surface complex, we developed a surface complexation model (in the basic Stern approximation) for the sorption of Cu onto birnessite. Using this model, we demonstrate that the concentration of inorganic Cu in the deep ocean should be several orders of magnitude lower than the observed total dissolved Cu. We propose that the observed total dissolved Cu concentration in the oceans reflects solubilization of Cu by microbially generated ligands. 相似文献