Sorption modelling on illite Part I: Titration measurements and the sorption of Ni, Co, Eu and Sn     

M.H. Bradbury 《Geochimica et cosmochimica acta》2009,73(4):990-1003

In this study the physico-chemical, titration and sorption characteristics of Na-illite du Puy (Na-illite) have been measured and modelled. Samples of illite, collected in the region of le Puy-en-Velay, France, were purified and conditioned to the Na-form and physico-chemically characterised. Potentiometric titrations on suspensions of the Na-illite were carried out using a batch backtitration technique in 0.01, 0.1 and 0.5 M NaClO₄ background electrolytes from pH∼3 to ∼11.5 in an inert atmosphere glove box. The supernatant solutions from each titration experiment in each series were analysed for K, Mg, Ca, Sr, Si, Al, Fe and Mn. The titration data were modelled in terms of the protolysis of two amphoteric edge sites (S^W1OH and S^W2OH) without an electrostatic term. Sorption edges (solid/liquid distribution ratios versus pH at trace sorbate concentrations and constant ionic strength) were determined for the transitions metals Ni(II) and Co(II), the lanthanide Eu(III), and the heavy metal Sn(IV) on Na-illite with NaClO₄ as the background electrolyte under anoxic conditions (CO₂ ? 2 ppm, O₂ ? 2 ppm). The study thus encompasses a broad range of metals with different thermodynamic characteristics and with valence states ranging from II to IV. The results from the modelling of the titration data, in combination with a non electrostatic surface complexation and cation exchange sorption model were applied to quantitatively describe the uptake characteristics of the metals listed above on Na-illite. Since sorption edges were measured at trace concentrations, metal uptake was modelled as occurring on strong type sites (S^SOH) only. This sorption model, the two site protolysis non electrostatic surface complexation and cation exchange model (2SPNE SC/CE model) had been previously developed and used to describe metal uptake on montmorillonite.  相似文献   

Investigation of the different binding edge sites for Zn on montmorillonite using P-EXAFS - The strong/weak site concept in the 2SPNE SC/CE sorption model     

Rainer Dähn  Bart Baeyens  Michael H. Bradbury 《Geochimica et cosmochimica acta》2011,75(18):5154-5168

The 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model has been used over the past decade or so to quantitatively describe the uptake of metals with oxidation states from II to VI on 2:1 clay minerals; montmorillonite and illite. One of the main features in this model is that there are two broad categories of amphoteric edge sorption sites; the so called strong (S^SOH) and weak (S^W1OH) sites. Because of their different sorption characteristics, it was expected that the coordination environments of the surface complexes on the two site types would be different. Zn isotherm data on two montmorillonites, Milos and STx-1, were measured and modelled using the 2SPNE SC/CE sorption model. The results were used to define the most favourable experimental conditions under which Zn sorption was either dominated by the strong (S^SOH, ∼2 mmol kg⁻¹) or by the weak sites (S^W1OH, ∼40 mmol kg⁻¹). Highly oriented self-supporting films were prepared for polarised extended X-ray absorption fine structure (P-EXAFS) investigations.Montmorillonites often contain Zn incorporated in the clay matrix. The Zn bound in this form was quantified and the results from the analysis of the P-EXAFS spectra were taken into account in the interpretation of the spectra measured at low Zn loadings (∼2 mmol kg⁻¹) and medium Zn loadings (∼30 mmol kg⁻¹). The Zn spectra on the “strong sites” exhibited a pronounced angular dependency and formed surface complexes in the continuity of the Al-octahedral sheets at the montmorillonite edges. In contrast, the Zn “weak site” spectra showed only a weak angular dependency. The spectroscopic evidence indicates the existence of two distinct groups of edge surface binding sites which is consistent with a multi-site sorption model and in particular with the strong/weak site concept intrinsic to the 2SPNE S/CE sorption model.  相似文献   

Predicting the uptake of Cs,Co, Ni,Eu, Th and U on argillaceous rocks using sorption models for illite     

《Applied Geochemistry》2015

Reliable predictions of radiocontaminant migration are a requirement for the establishment of radioactive waste repositories. Parametrization of the necessary sorption models seems to be, however, extremely challenging given the multi-mineralic composition of the lithosphere. In this study it is shown for two argillaceous rocks – Boda and Opalinus Clay relevant for the Hungarian and Swiss repository concepts, respectively – that this task can be substantially simplified by taking into account only the most sorptive mineral fraction, namely the 2:1 clay minerals illite and illite/smectite mixed layers. Two different models were required to blind predict the sorption isotherms of Cs, Co, Ni, Eu, Th and UO₂ measured on the two clay rock samples in a synthetic porewater. Cs sorption was modelled with the generalised Cs (GCs) sorption model and the sorption of the other cations with the 2 site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model. The 2SPNE SC/CE model for illite was extended with surface complexation reactions on weak sites for Co, Ni, Eu, UO₂ and on strong sites for Eu-carbonato complexes. Complementary to the sorption measurements and modelling, extended X-ray absorption fine structure (EXAFS) spectroscopy was used to probe the retention mechanism of Ni on illite, Boda and Opalinus Clay at higher loadings. The reliable blind predictions of the selected metal cations, which are representative for monovalent alkaline metals, divalent transition metals, lanthanides, and trivalent, tetravalent and hexavalent actinides, confirms the applicability of this simplified bottom up approach, and, renders the underlying sorption models particularly useful to predict sorption for the wide range of cations to be considered in the safety analysis of radioactive waste repositories in clay-rich environments.  相似文献   

Sorption of Eu(III)/Cm(III) on Ca-montmorillonite and Na-illite. Part 2: Surface complexation modelling     

M.H. Bradbury  B. Baeyens  Th. Rabung 《Geochimica et cosmochimica acta》2005,69(23):5403-5412

Sorption edges and isotherms for Eu(III) uptake on Ca-montmorillonite and Na-illite in 0.066 mol/L Ca(ClO₄)₂ and 0.1 mol/L NaClO₄ background electrolytes, respectively, were modelled using a quasi-mechanistic sorption model (the two site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model). For both clay minerals the Eu sorption edges could be quantitatively modelled in the pH range ∼3 to ∼10 using cation exchange reactions for Eu³⁺/Na⁺ and Eu³⁺/Ca²⁺ and three surface complexation reactions on the strong sorption sites forming ≡S^SOEu²⁺, ≡S^SOEuOH⁺ and ≡S^SOEu(OH)₂° inner sphere complexes which appear successively with increasing pH. Time resolved laser fluorescence spectroscopy (TRLFS) measurements of Cm(III) loaded Ca-montmorillonite and Na-illite were available from Part 1 of this work. De-convolution of the normalised fluorescence spectra measured at different pH values indicated three distinct Cm surface complexes, Cm complexes 1, 2 and 3 for both clay minerals, in agreement with model predictions, but with different distribution functions for the individual species. Under the assumption that Eu and Cm exhibit essentially the same hydrolysis and sorption behaviour, the Eu surface complexation constants were used to predict surface species distribution functions for Cm under the same experimental conditions used in the TRLFS measurements. Comparison of modelled and experimentally deduced species distributions indicated that for both clay minerals peak heights and widths of the three peaks did not correspond particularly well. It is shown that the calculated species distribution functions are sensitive to the values of the hydrolysis constants used in the calculations, whereas modelling the sorption edge measurements by applying the 2SPNE SC/CE approach is much less sensitive. By modifying the values of the hydrolysis constants within their uncertainty range and re-modelling the sorption edges, considerably better correspondence between the modelled and TRLFS species distribution functions was found. In particular, peak positions, heights and widths for the model predicted peaks for the ≡S^SOCm²⁺ and ≡S^SOCmOH⁺ species distribution, and those for Cm complexes 1 and 2 derived from TRLFS, were found to be very close for both clay minerals. However, discrepancies were still apparent between the profile for the calculated ≡S^SOEu(OH)₂° surface species and the Cm complex 3 species, especially in the case of Na-illite.  相似文献   

Experimental and modelling studies of caesium sorption on illite     

《Geochimica et cosmochimica acta》1999,63(19-20):3217-3227

A natural illite (illite du Puy) was purified and converted to the homo-ionic Na form. The conditioned Na–illite was characterised in terms of its mineralogy, chemical inventory, and surface properties. The structural formula was determined from EDS analyses (SEM/TEM) and bulk chemistry. A cation exchange capacity of 127 mEq/kg was determined by the Na isotope dilution method at neutral pH.The sorption of Cs was measured as a function of NaClO₄ background electrolyte concentration (1.0, 0.1 and 0.01 M), Cs concentration and pH in the range ≈3 to ≈10. Before obtaining these measurements the kinetics of Cs uptake were determined at initial concentrations of 2 × 10⁻⁸ M and 7 × 10⁻⁵ M, representing the extremes of the range investigated, and was found to be concentration dependent. The supernatant solutions after centrifugation were analysed for major cations in all of the sorption tests.A two-site cation exchange model was developed to describe the sorption of Cs over the whole range of experimental conditions. The two-site types were termed frayed edge sites, FES (high affinity/low capacity) and type II sites (low affinity/high capacity). At low NaClO₄ concentrations, Cs sorption decreased at pH values less than neutral. This was interpreted in terms of competitive effects from H, and K released by the partial dissolution of illite, which cannot be avoided at low and high pH values. Selectivity coefficient values for Cs–Na, Cs–K, K–Na, and H–Na exchange equilibria on the FES sites, and Cs–Na exchange on the type II sites are given for illite together with the corresponding site capacities.  相似文献   

Modelling colloid association with plutonium: The effect of pH and redox potential     

Claude Degueldre  Magdalena Bolek 《Applied Geochemistry》2009,24(2):310-318

An analytical expression that evaluates the effect of pH and the redox potential (E) on Pu-colloid association was studied on a model basis. It includes surface complexation with one type of surface site and its formulation leads to a distribution coefficient (K_d) as a function of the pH (hydrolysis) and E (redox sensitive species). The formulation also considers the values of the stability and hydrolysis constants for all species present in solution and associated at the surface. Correlations between hydrolysis and surface complexation constants reported in the literature have been applied systematically to evaluate sorption of all species for each colloid system. The presence of ligands in solution was also taken into account. The model was applied to study the association of Pu onto colloids coated with AlOH, FeOH or SiOH groups in the presence and in the absence of carbonates in solution. The tests performed with the model suggest that the oxidation of Pu(III) to Pu(IV) has the potential to increase sorption, as demonstrated by the increased K_d values. Under natural conditions Pu may be present at oxidation states of (III)--(VI), and the effect of redox potential is significant because of the differences in the sorption of each oxidation state. When carbonates are present in the solution, the calculated values of distribution coefficient were lower than those calculated in the absence of carbonates, particularly in the case of Pu(VI). The K_d values obtained with the developed model are compared with experimental values reported for the sorption of Pu onto colloids. This model can equally be applied to study the sorption of other redox sensitive elements.  相似文献   

Sorption of Eu on Na- and Ca-montmorillonites: experimental investigations and modelling with cation exchange and surface complexation     

M.H Bradbury  B Baeyens 《Geochimica et cosmochimica acta》2002,66(13):2325-2334

The 2-site protolysis no electrostatics surface complexation and cation exchange (2SPNE/CE) model used in previous work to model the sorption of Ni and Zn on Na- and Ca-montmorillonites was applied to sorption edges and isotherms measured for Eu on these two montmorillonite forms. The aim was to further test the applicability of the sorption model on a trivalent element with a more complex aqueous chemistry. An additional reason for choosing Eu was that it is considered to be a good chemical analogue for other lanthanides and trivalent actinides. With site types, site capacities, and protolysis constants fixed at the values in the Ni/Zn studies, all of the measured sorption edge data could be modelled using cation exchange and the monodentate surface species, ≡S^SOEu²⁺, ≡S^SOEuOH⁺ and ≡S^SOEu(OH)₃⁻, on the strong site type. However, an additional modelling study showed that the same data were almost equally well described by considering bidentate surface complexes, (≡S^SO)₂Eu⁺ and (≡S^SO)₂Eu(OH)₂⁻, and cation exchange. To model the sorption isotherm measurements up to pH = 7.2, only one additional weak site surface complex was required, ≡S^W1OEu²⁺ for the monodentate case and (≡S^W1O)₂Eu⁺ for the bidentate case. Selectivity coefficients are given for Eu³⁺- Ca²⁺ and Eu³⁺- Na⁺ exchange on the planar sites and surface complexation constants for monodentate and bidentate Eu surface species on the edge sites of montmorillonite.  相似文献   

Linear Free Energy Relationships for Metal-Ligand Complexation: Bidentate Binding to Negatively-Charged Oxygen Donor Atoms     

Carbonaro RF  Atalay YB  Di Toro DM 《Geochimica et cosmochimica acta》2011,75(9):2499-10090

Stability constants for metal complexation to bidentate ligands containing negatively-charged oxygen donor atoms can be estimated from the following linear free energy relationship (LFER): log K_ML = χ_OO(α_O log K_HL,1 + α_O log K_HL,2) where K_ML is the metal-ligand stability constant for a 1:1 complex, K_HL,1 and K_HL,2 are the proton-ligand stability constants (the ligand pK_a values), and α_O is the Irving-Rossotti slope. The parameter χ_OO is metal specific and has slightly different values for five and six membered chelate rings. LFERs are presented for 21 different metal ions and are accurate to within approximately 0.30 log units in predictions of log K_ML values. Ligands selected for use in LFER development include dicarboxylic acids, carboxyphenols, and ortho-diphenols. For ortho-hydroxybenzaldehydes, α-hydroxycarboxylic acids, and α-ketocarboxylic acids, a modification of the LFER where log K_HL,2 is set equal to zero is required. The chemical interpretation of χ_OO is that it accounts for the extra stability afforded to metal complexes by the chelate effect. Cu-NOM binding constants calculated from the bidentate LFERs are similar in magnitude to those used in WHAM 6. This LFER can be used to make log K_ML predictions for small organic molecules. Since natural organic matter (NOM) contains many of the same functional groups (i.e. carboxylic acids, phenols, alcohols), the LFER log K_ML predictions shed light on the range of appropriate values for use in modeling metal partitioning in natural systems.  相似文献   

Constantes de stabilité de complexes organo-minéraux. Interactions des ions plombeux avec les composés organiques hydrosolubles des eaux gravitaires de podzol     

Y Bizri  M Cromer  J.P Scharff  B Guillet  J Rouiller 《Geochimica et cosmochimica acta》1984,48(2):227-234

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Blind prediction of Cu(II) sorption onto goethite: Current capabilities of diffuse double layer model     

Anke Richter  Vinzenz Brendler  Cordula Nebelung 《Geochimica et cosmochimica acta》2005,69(11):2725-2734

The paper presents examples illustrating the current blind predictive capabilities of the diffuse double layer model (DDLM) as the model requiring the smallest set of parameters and thus being most suitable for substituting even more empiric sorption approaches such as distribution coefficients K_D. The general strategy for the selection of numerical data are discussed. Based on the information about the minerals compiled in the sorption database RES³T (Rossendorf Expert System for Surface and Sorption Thermodynamics), first a set of relevant surface species is generated. Then relevant surface complexation parameters are taken from RES³T: the binding site density for the minerals, the surface protolysis constants, and the stability constants for all relevant surface complexes. To be able to compare and average thermodynamic constants originating from different sources, a normalization concept is applied.Our demonstration is based on a blind prediction exercise, i.e., the goal was not to provide optimal fits. The system considered is Cu(II) sorption onto goethite. The predictions are compared with raw data from three independent experimental investigations. The calculations were performed with the FITEQL 3.2 code. In most cases the model predictions represented the experimental sorption values for the sorbed amount of Cu(II), expressed as conventional distribution coefficients, within one order of magnitude or better.We conclude that the application of DDLM can indeed be used for estimating distribution coefficients for contaminants in well defined mineral systems. A stepwise strategy of species selection, data collection, normalization, and averaging is outlined. The SCM database so far assembled within the RES³T project is able to provide the parameter sets.  相似文献   

Iron isotope fractionation and atom exchange during sorption of ferrous iron to mineral surfaces     

Christian Mikutta  Jan G. Wiederhold  Olaf A. Cirpka  Bernard Bourdon 《Geochimica et cosmochimica acta》2009,73(7):1795-1526

The application of stable Fe isotopes as a tracer of the biogeochemical Fe cycle necessitates a mechanistic knowledge of natural fractionation processes. We studied the equilibrium Fe isotope fractionation upon sorption of Fe(II) to aluminum oxide (γ-Al₂O₃), goethite (α-FeOOH), quartz (α-SiO₂), and goethite-loaded quartz in batch experiments, and performed continuous-flow column experiments to study the extent of equilibrium and kinetic Fe isotope fractionation during reactive transport of Fe(II) through pure and goethite-loaded quartz sand. In addition, batch and column experiments were used to quantify the coupled electron transfer-atom exchange between dissolved Fe(II) (Fe(II)_aq) and structural Fe(III) of goethite. All experiments were conducted under strictly anoxic conditions at pH 7.2 in 20 mM MOPS (3-(N-morpholino)-propanesulfonic acid) buffer and 23 °C. Iron isotope ratios were measured by high-resolution MC-ICP-MS. Isotope data were analyzed with isotope fractionation models. In batch systems, we observed significant Fe isotope fractionation upon equilibrium sorption of Fe(II) to all sorbents tested, except for aluminum oxide. The equilibrium enrichment factor, , of the Fe(II)_sorb-Fe(II)_aq couple was 0.85 ± 0.10‰ (±2σ) for quartz and 0.85 ± 0.08‰ (±2σ) for goethite-loaded quartz. In the goethite system, the sorption-induced isotope fractionation was superimposed by atom exchange, leading to a δ^56/54Fe shift in solution towards the isotopic composition of the goethite. Without consideration of atom exchange, the equilibrium enrichment factor was 2.01 ± 0.08‰ (±2σ), but decreased to 0.73 ± 0.24‰ (±2σ) when atom exchange was taken into account. The amount of structural Fe in goethite that equilibrated isotopically with Fe(II)_aq via atom exchange was equivalent to one atomic Fe layer of the mineral surface (∼3% of goethite-Fe). Column experiments showed significant Fe isotope fractionation with δ^56/54Fe(II)_aq spanning a range of 1.00‰ and 1.65‰ for pure and goethite-loaded quartz, respectively. Reactive transport of Fe(II) under non-steady state conditions led to complex, non-monotonous Fe isotope trends that could be explained by a combination of kinetic and equilibrium isotope enrichment factors. Our results demonstrate that in abiotic anoxic systems with near-neutral pH, sorption of Fe(II) to mineral surfaces, even to supposedly non-reactive minerals such as quartz, induces significant Fe isotope fractionation. Therefore we expect Fe isotope signatures in natural systems with changing concentration gradients of Fe(II)_aq to be affected by sorption.  相似文献   

Effects of pH on isotherm modeling and cation competition for Cd(II) and Cu(II) biosorption on Myriophyllum spicatum from aqueous solutions     

Guoxin Li  Dandan Zhang  Qingsong Li  Guoyuan Chen 《Environmental Earth Sciences》2014,72(11):4237-4247

The biosorption characteristics of Cd(II) and Cu(II) ions from aqueous solutions obtained using submerged aquatic plant (Myriophyllum spicatum) biomass were investigated in terms of equilibrium, kinetics, thermodynamics, and cation competition. Langmuir and Freundlich models were applied to describe the biosorption isotherm of metal ions by M. spicatum biomass and isotherm constants considering the most important parameter, pH. The variation of sorption isotherm constants showed pH dependence. The Langmuir and Freundlich models fitted the equilibrium data well. The maximum biosorption capacity (q _m) of M. spicatum biomass was determined to be 29.07 mg/g for the Cd(II) ion at pH 5.0 and 12.12 mg/g for the Cu(II) ion at pH 6.0. Chi square analysis showed that the Freundlich model fitted the equilibrium data better than the Langmuir isotherm. Competition of Cd(II) and Cu(II) in a binary solution showed that the Langmuir monolayer capacity of Cd(II) decreased from 29.07 mg/g with only Cd(II) in solution to 12.02 mg/g in the presence of Cu(II). Kinetics results showed that the biosorption processes of both metal ions followed the pseudo-second-order kinetics well. The calculated thermodynamic parameters (?G ⁰, ?H ⁰, and ?S ⁰) showed that biosorption of Cd(II) and Cu(II) ions onto M. spicatum biomass was feasible, spontaneous, and endothermic in nature. Fourier transform infrared spectroscopy spectrum analysis revealed that Cd(II) and Cu(II) sorption was mainly ascribed to carboxyl, hydroxyl, amine, and C–N groups in M. spicatum.  相似文献   

Diffusion and sorption of Cs, I and HTO in samples of the argillaceous Wakkanai Formation from the Horonobe URL, Japan: Clay-based modeling approach     

Yukio Tachi  Kenji Yotsuji  Yoshimi Seida  Mikazu Yui 《Geochimica et cosmochimica acta》2011,75(22):6742-6759

Diffusion and sorption behaviors of cationic Cs⁺, anionic I⁻ and neutral HTO in samples of the Wakkanai Formation from the Horonobe underground research laboratory (URL), Japan, were investigated as a function of ionic strength (I) of synthetic groundwater by through-diffusion and batch sorption experiments and mechanistic modeling. The effective diffusivities (D_e) measured by through-diffusion experiments showed cation excess and anion exclusion effects, which were strongly dependent on I; D_e for Cs⁺ decreased as I increased, D_e for I⁻ showed the opposite dependency and D_e for HTO showed no dependence. The sorption of Cs⁺ measured by through-diffusion and batch sorption experiments were described by Freundlich isotherms with consistent parameters and decreased with I as a result of competitive ion exchange.Diffusion and sorption behaviors were interpreted by assuming the clay components of illite and smectite control diffusion and sorption mechanisms. The component additive (CA) sorption model, which includes illite and smectite contents and their ion exchange constants, provided a reasonable account of the Cs⁺ sorption trends measured as functions of I and Cs concentration. The diffusion model was developed by coupling the electrical double layer (EDL) model, describing the change of ionic concentrations (cation excess and anion deficit) and viscoelectric effects caused by electrostatic interaction at negatively charged clay surfaces, and a simplified pore model assuming one type of pore shape and includes their size distribution. When averaging the electrostatic effects by using the pore surface area distribution, the model could predict the cation excess and anion exclusion effects, and its dependence on I reasonably well. This result implies the nanoscale pores dominating the pore surface area can strongly impact on ionic diffusion in argillaceous rocks. The clay-based modeling approach described here provides a useful tool to predict ionic diffusion and sorption in argillaceous rocks.  相似文献   

The sorption behaviour of caesium on Opalinus Clay: A comparison between intact and crushed material     

L.R. Van Loon  B. BaeyensM.H. Bradbury 《Applied Geochemistry》2009

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Surface complexation modelling of Cd(II), Cu(II), Ni(II), Pb(II) and Zn(II) adsorption onto kaolinite     

Xueyuan Gu  Les J. Evans 《Geochimica et cosmochimica acta》2008,72(2):267-276

Proton binding constants for the edge and basal surface sites of kaolinite were determined by batch titration experiments at 25 °C in the presence of 0.1 M, 0.01 M and 0.001 M solutions of NaNO₃ and in the pH range 3-9. By optimizing the results of the titration experiments, the ratio of the edge sites to the basal surface sites was found to be 6:1. The adsorption of Cd(II), Cu(II), Ni(II), Zn(II) and Pb(II) onto kaolinite suspensions was investigated using batch adsorption experiments and results suggested that in the lower pH range the metallic cations were bound through non-specific ion exchange reactions on the permanently charged basal surface sites (X⁻). Adsorption on these sites was greatly affected by ionic strength. With increasing pH, the variable charged edge sites (SOH) became the major adsorption sites and inner-sphere specifically adsorbed monodentate complexes were believed to be formed. The effect of ionic strength on the extent of adsorption of the metals on the variable charged edge sites was much less than those on the permanently charged sites. Two binding constants, log K_(X2Me) and log K_(SOMe), were calculated by optimizing these constants in the computer program FITEQL. A model combining non-specific ion exchange reactions and inner-sphere specific surface complexations was developed to predict the adsorption of heavy metals onto kaolinite in the studied pH range. Linear free energy relationships were found between the edge site binding constants and the first hydrolysis constants of the metals.  相似文献   

The influence of Fe(II) competition on the sorption and migration of Ni(II) in MX-80 bentonite     

Wilfried Pfingsten  Mike BradburyBart Baeyens 《Applied Geochemistry》2011,26(8):1414-1422

The results from batch sorption experiments on montmorillonite systems have demonstrated that bivalent transition metals compete with one another for sorption sites. For safety analysis studies of high level radioactive waste repositories with compacted bentonite near fields, the importance of competitive sorption on the migration of radionuclides needs to be evaluated. Under reducing conditions, the bentonite porewater chosen has a Fe(II) concentration of ∼5.3 × 10⁻⁵ M through saturation with siderite. The purpose of this paper is to assess the influence of such high Fe(II) concentrations on the transport of Ni(II) through compacted bentonite, Ni(II) was chosen as an example of a bivalent transition metal. The one-dimensional calculations were carried out at different Ni(II) equilibrium concentrations at the boundary (Ni(II)_EQBM) with the reactive transport code MCOTAC incorporating the two site protolysis non electrostatic surface complexation/cation exchange sorption model, MCOTAC-sorb. At a Ni(II)_EQBM level of 10⁻⁷ M without Fe(II) competition, the reactive transport calculations using a constant K_d approach and the MCOTAC-sorb calculation yielded the same breakthrough curves. At higher Ni(II)_EQBM (10⁻⁵ M), the model calculations with MCOTAC-sorb indicated a breakthrough which was shifted to later times by a factor of ∼5 compared with the use of the constant K_d approach.When sorption competition was included in the calculations, the magnitude of the influence depended on the sorption characteristics of the two competing sorbates and their respective concentrations. At background Fe(II) concentrations of 5.3 × 10⁻⁵ M, and a Ni(II)_EQBM level of 10⁻⁷ M, the Ni(II) breakthrough time was ∼15 times earlier than in the absence of competition. At such Fe(II) concentrations the Ni(II) breakthrough curves at all source concentrations less than 3.5 × 10⁻⁵ M (fixed by the NiCO_3,S solubility limit) are the same i.e. Ni(II) exhibits linear (low) sorption.Competitive sorption effects can have significant influences on the transport of radionuclides through compacted bentonite i.e. reduce the migration rates. Since, for the case considered here, the Fe(II) concentration in the near field of a high-level radioactive waste repository may change in time and space, the transport of bivalent transition metal radionuclides can only be properly modelled using a multi-species reactive transport code which includes a sorption model.  相似文献   

A Donnan potential model for metal sorption onto Bacillus subtilis     

Nathan Yee  David A. Fowle 《Geochimica et cosmochimica acta》2004,68(18):3657-3664

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 (Ψ_DON) 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 K₂^int 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   

Europium retention onto clay minerals from 25 to 150 °C: Experimental measurements, spectroscopic features and sorption modelling     

E. Tertre  G. Berger  S. Castet  M. Loubet 《Geochimica et cosmochimica acta》2006,70(18):4563-4578

The sorption of Eu(III) onto kaolinite and montmorillonite was investigated up to 150 °C. The clays were purified samples, saturated with Na in the case of montmorillonite. Batch experiments were conducted at 25, 40, 80 and 150 °C in 0.5 M NaClO₄ solutions to measure the distribution coefficients (Kd) of Eu as a trace element (<10⁻⁶ mol/L) between the solution and kaolinite. For the Na-montmorillonite, we used Kd results from a previous study [Tertre, E., Berger, G., Castet, S., Loubet, M., Giffaut, E., 2005. Experimental study of adsorption of Ni²⁺, Cs⁺ and Ln³⁺ onto Na-montmorillonite up to 150 °C. Geochim. Cosmochim. Acta69, 4937-4948] obtained under exactly the same conditions. The number and nature of the Eu species sorbed onto both clay minerals were investigated by time resolved laser fluorescence spectroscopy (TRLFS) in specific experiments in the same temperature range. We identified a unique inner-sphere complex linked to the aluminol sites in both clays, assumed to be AlOEu²⁺ at the edge of the particles, and a second exchangeable outer-sphere complex for montmorillonite, probably in an interlayer position. The Kd values were used to adjust the parameters of a surface complexation model (DLM: diffuse layer model) from 25 to 150 °C. The number of Eu complexes and the stoichiometry of reactions were constrained by TRLFS. The acidity constants of the amphoteric aluminol sites were taken from another study [Tertre, E., Castet, S., Berger, G., Loubet, M., Giffaut, E. Acid/base surface chemistry of kaolinite and Na-montmorillonite at 25 and 60 °C: experimental study and modelling. Geochim. Cosmochim. Acta, in press], which integrates the influence of the negative structural charge of clays on the acid/base properties of edge sites as a function of temperature and ionic strength. The results of the modelling show that the observed shift of the sorption edge towards low pH with increasing temperature results solely from the contribution of the AlOEu²⁺ edge complexes. Finally, we successfully tested the performance of our model by confronting the predictions with experimental Kd data. We used our own data obtained at lower ionic strength (previous study) or higher suspension density and higher starting concentration (TRLFS runs, this study), as well as published data from other experimental studies [Bradbury, M.H., Baeyens, B., 2002. Sorption of Eu on Na and Ca-montmorillonite: experimental investigations and modeling with cation exchange and surface complexation. Geochim. Cosmochim. Acta66, 2325-2334; Kowal-Fouchard, A., 2002. Etude des mécanismes de rétention des ions U(IV) et Eu(III) sur les argiles: influence des silicates. Ph.D. Thesis, Université Paris Sud, France, 330p].  相似文献   

Surface complexation of U(VI) on goethite (α-FeOOH)     

David M. Sherman  Caroline L. Peacock  Christopher G. Hubbard 《Geochimica et cosmochimica acta》2008,72(2):298-310

Sorption of U(VI) to goethite is a fundamental control on the mobility of uranium in soil and groundwater. Here, we investigated the sorption of U on goethite using EXAFS spectroscopy, batch sorption experiments and DFT calculations of the energetics and structures of possible surface complexes. Based on EXAFS spectra, it has previously been proposed that U(VI), as the uranyl cation , sorbs to Fe oxide hydroxide phases by forming a bidentate edge-sharing (E2) surface complex, >Fe(OH)₂UO₂(H₂O)_n. Here, we argue that this complex alone cannot account for the sorption capacity of goethite (α-FeOOH). Moreover, we show that all of the EXAFS signal attributed to the E2 complex can be accounted for by multiple scattering. We propose that the dominant surface complex in CO₂-free systems is a bidentate corner-sharing (C2) complex, (>FeOH)₂UO₂(H₂O)₃ which can form on the dominant {101} surface. However, in the presence of CO₂, we find an enhancement of UO₂ sorption at low pH and attribute this to a (>FeO)CO₂UO₂ ternary complex. With increasing pH, U(VI) desorbs by the formation of aqueous carbonate and hydroxyl complexes. However, this desorption is preceded by the formation of a second ternary surface complex (>FeOH)₂UO₂CO₃. The three proposed surface complexes, (>FeOH)₂UO₂(H₂O)₃, >FeOCO₂UO₂, and (>FeOH)₂UO₂CO₃ are consistent with EXAFS spectra. Using these complexes, we developed a surface complexation model for U on goethite with a 1-pK model for surface protonation, an extended Stern model for surface electrostatics and inclusion of all known UO₂-OH-CO₃ aqueous complexes in the current thermodynamic database. The model gives an excellent fit to our sorption experiments done in both ambient and reduced CO₂ environments at surface loadings of 0.02-2.0 wt% U.  相似文献