Geochemical and thermodynamic aspects of sorption of strontium on kaolinite dominated clay samples at Kalpakkam

The mobility of strontium in subsurface is largely influenced by sorption on to clay minerals. In the present study, kaolinite clay samples collected from the Kalpakkam nuclear plant site were employed to understand the sorption characteristics of strontium by batch method. The effect of several parameters such as time, strontium ion concentration, pH, temperature and ionic strength was investigated. The kinetic studies suggested pseudo-second-order mechanism. The experimental sorption data was fitted to Langmuir adsorption model for obtaining the sorption capacity of the sorbent. The maximum sorption capacity was 5.77 mg/g at 298 K and was found to increase with an increase in temperature. It was observed that the distribution coefficient (K _d) of strontium on clay increased as the pH of the solution increased. The distribution coefficient was found to decrease with an increase in concentration of Na⁺ and Ca²⁺ ions. This variation of K _d suggests that cation exchange is the predominant sorption process. It was also observed that sorption process is endothermic. The thermodynamic parameters such as ∆G ⁰, ∆H ⁰ and ∆S ⁰ were calculated. The negative values obtained for ∆G ⁰ indicated that the sorption of strontium on clay was spontaneous at all studied concentrations. ∆G ⁰ becomes more negative with an increase in temperature, suggests that the sorption process is more favorable at higher temperatures.     

Interaction of bentonite colloids with Cs, Eu, Th and U in presence of humic acid: A flow field-flow fractionation study

The interaction of Cs(I), Eu(III), Th(IV) and U(VI) with montmorillonite colloids was investigated in natural Grimsel Test Site groundwater over a 3 years period. The asymmetric flow field-flow fractionation combined with various detectors was applied to study size variations of colloids and to monitor colloid association of trace metals. The colloids suspended directly in the low ionic strength (I), slightly alkaline granitic groundwater (I = 10⁻³ mol/L, pH 9.6) showed a gradual agglomeration with a size distribution shift from initially 10-200 nm to 50-400 nm within over 3 years. The Ca²⁺ concentration of 2.1 × 10⁻⁴ mol/L in the ground water is believed to be responsible for the slow agglomeration due to Ca²⁺ ion exchange against Li⁺ and Na⁺ at the permanently charged basal clay planes. Furthermore, the Ca²⁺ concentration lies close to the critical coagulation concentration (CCC) of 10⁻³ mol L⁻¹ for clay colloids. Slow destabilization may delimit clay colloid migration in this specific groundwater over long time scales. Eu(III) and Th(IV) are found predominantly bound to clay colloids, while U(VI) prevails as the UO₂(OH)₃⁻ complex and Cs(I) remains mainly as aquo ion under our experimental conditions. Speciation calculations qualitatively represent the experimental data. A focus was set on the reversibility of metal ion-colloid binding. Addition of humic acid as a competing ligand induces rapid metal ion dissociation from clay colloids in the case of Eu(III) even after previous aging for about 3 years. Interestingly only partial dissociation occurs in the case of Th(IV). Experiments and calculations prove that the humate complexes dominate the speciation of all metal ions under given conditions. The partial irreversibility of clay bound Th(IV) is presently not understood but might play an important role for the colloid-mediated transport of polyvalent actinides over wide distances in natural groundwater.     

Phosphorus adsorption characteristics at the sediment–water interface and relationship with sediment properties in FUSHI reservoir, China

This study was designed to survey the reservoir sediment properties, assess the phosphorus (P) sorption isotherm, and analyze the relationship between sediment properties and sorption parameters. Physicochemical analysis indicated that sediment from the FUSHI reservoir in Zhejiang Province, China, has similar physical and chemical properties and has been contaminated by P. Sorption isotherm experiments showed that the sorption process could be described by Langmuir and Freundlich models. The parameters of Q _max (Phosphorus sorption maximum) and K (Freundlich adsorption isotherm constant) ranged from 618.98 to 825.70?mg?kg^?1 and 114.18 to 170.74?l?kg^?1, respectively. EPC₀ (zero P equilibrium concentration) ranged from 0.14 to 0.24?mg?l^?1, more than the total P concentration in the water of the reservoir. Thus, the reservoir sediment releases P into the water and acts as a ??P resource??. The clay, Fe_o, Al_t, and Fe_t?+?Al_t content were the main active components in P sorption. Q _max had a highly significant positive relationship with some properties and could be estimated by a combination of these.     

Thermochemical study of natural montmorillonite

The paper reports results of an experimental thermochemical study (in a heat-flux Tian-Calvet microcalorimeter) of montmorillonite from (I) the Taganskoe and (II) Askanskoe deposits and (III) from the caldera of Uzon volcano, Kamchatka. The enthalpy of formation Δ _f H _el ⁰ (298.15 K) of dehydrated hydroxyl-bearing montmorillonite was determined by melt solution calorimetry: ?5677.6 ± 7.6 kJ/mol for Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ (I), ?5614.3 ± 7.0 kJ/mol for Na_0.4K_0.1(Ca_0.1Mg_0.3Al_1.5Fe _0.1 ³⁺ )[Si_3.9Al_0.1O₁₀](OH)₂ (II), ?5719 ± 11 kJ/mol for K_0.1Ca_0.2Mg_0.2(Mg_0.6Al_1.3Fe _0.1 ³⁺ ) [Si_3.7Al_0.3O10](OH)₂ (III), and ?6454 ± 11 kJ/mol for water-bearing montmorillonite (I) Na_0.3Ca_0.1(Mg_0.4Al_1.6)[Si_3.9Al_0.1O₁₀](OH)₂ · 2.6H₂O. The paper reports estimated enthalpy of formation for the smectite end members of the theoretical composition of K-, Na-, Mg-, and Ca-montmorillonite and experimental data on the enthalpy of dehydration (14 ± 2 kJ per mole of H₂O) and dehydroxylation (166 ± 10 kJ per mole of H₂O) for Na-montmorillonite.     

Insight into adsorption equilibrium,kinetics and thermodynamics of lead onto alluvial soil

In the present study, adsorption of lead (II) ions from aqueous solution by alluvial soil of Bhagirathi River was investigated under batch mode. The influence of solution pH, sorbent dose, initial lead (II) concentration, contact time, stirring rate and temperature on the removal process were investigated. The lead adsorption was favored with maximum adsorption at pH 6.0. Sorption equilibrium time was observed in 60 min. The equilibrium adsorption data were analyzed by the Freundlich, Langmuir, Dubinin–Radushkevich and Temkin adsorption isotherm models. The kinetics of lead (II) ion was discussed by pseudo first-order, pseudo second-order, intra-particle diffusion, and surface mass transfer models. It was shown that the adsorption of lead ions could be described by the pseudo second-order kinetic model. The activation energy of the adsorption process (E _a) was found to be ?38.33 kJ mol^?1 using the Arrhenius equation, indicating exothermic nature of lead adsorption onto alluvial soil. Thermodynamic parameters, such as Gibbs free energy (?G ⁰), the enthalpy (?H ⁰), and the entropy change of sorption (?S ⁰) have also been evaluated and it has been found that the adsorption process was spontaneous, feasible, and exothermic in nature. The results indicated that alluvial soil of Bhagirathi River can be used as an effective and low cost adsorbent to remove lead ions from aqueous solutions.     

Sorption of lead by chemically modified rice bran

In this work, the effectiveness of native and chemically modified rice bran to remove heavy metal Pb(II) ions from aqueous solution was examined. Chemical modifications with some simple and low-cost chemicals resulted in enhancement of the adsorption capacities and had faster kinetics than native rice bran. Experiments were conducted in shake flasks to monitor the upshot of parameters over a range of pH, initial Pb(II) concentrations and contact times using a batch model study. The sorption capacities q (mg g^?1) increased in the following order: NaOH (147.78), Ca(OH)₂ (139.08), Al(OH)₃ (127.24), esterification (124.28), NaHCO₃ (118.08), methylation (118.88), Na₂CO₃ (117.12) and native (80.24). The utmost uptake capacity q (mg g^?1) was shown by NaOH-pretreated rice bran. The results showed that, using NaOH-modified rice bran, the chief removal of Pb(II) was 74.54 % at pH 5, primary Pb(II) concentration 100 mg L^?1 and contact time 240 min. Equilibrium isotherms for the Pb(II) adsorption were analyzed by Langmuir and Freundlich isotherm models. The Langmuir isotherm model, showing Pb(II) sorption as accessible through the high value of the correlation coefficient (R ² = 0.993), showed a q _max value of 416.61 mg g^?1. The kinetic model illustrated adsorption rates well, depicted by a second order, which gives an indication concerning the rate-limiting step. Thermodynamic evaluation of the metal ion ?G ^o was carried out and led to the observation that the adsorption reaction is spontaneous and endothermic in nature. NaOH chemically modified rice bran was a superb biosorbent for exclusion of Pb(II) and proved to be excellent for industrial applications.     

Sorption characteristics and mechanisms of ammonium by coal by-products: slag, honeycomb-cinder and coal gangue

The adsorption behaviors of ammonium from aqueous solutions were investigated for three solid coal wastes, slag, honeycomb-cinder and coal gangue. The ammonium sorption processes were well modeled by the pseudo second-order model (R ² > 0.99). The experimental data were fitted to both the Langmuir model and the Freundlich model, with the Langmuir model better representing the data. The maximum ammonium sorption capacities calculated from the Langmuir model were 3.1, 5.0 and 6.0 mg/g for the slag, honeycomb-cinder and coal gangue samples, respectively. The pH value of the solution affected the ammonium removal, and the higher uptakes found in either neutral or alkaline conditions for the three materials. The thermodynamic parameters, ΔH, were calculated to be 29.75, 25.21 and 17.91 kJ/mol for the SL, HC and CG samples, respectively, with the positive values indicating that the ammonium sorption processes were endothermic. Based on the results, it can be concluded that coal gangue may have more potential for being used as a sorbent for the ammonium removal from wastewater among the three coal by-products.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: II. Mineral transformation and microscale partitioning

Microscopic and spectroscopic studies were conducted to assess mineral transformation processes in aqueous suspensions of illite (Il), vermiculite (Vm) and montmorillonite (Mt) that were subjected to weathering in a simulated high-level radioactive tank waste leachate (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs⁺ and Sr²⁺ present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻ mol kg⁻. Incongruent clay dissolution resulted in an accumulation of secondary aluminosilicate precipitates identified as nitrate-sodalite, nitrate-cancrinite and zeolite X, by molecular spectroscopy and electron microscopy (XRD, IR, NMR, SEM-EDS and TEM-EDS). Contaminant fate was dependent on competing uptake to parent clays and weathering products. TEM-EDS results indicated that high Il affinity for Cs was due to adsorption at frayed edge sites. The Il system also comprised Sr-rich aluminous precipitates after 369 d reaction time. In Mt systems, Cs and Sr were co-precipitated into increasingly recalcitrant spheroidal precipitates over the course of the experiment, whereas contaminant association with montmorillonite platelets was less prevalent. In contrast, Cs and Sr were found in association with weathered Vm particles despite the formation of spheroidal aluminosilicate precipitates that were comparable to those formed from Mt dissolution.     

Lanthanide sorption on smectitic clays in presence of cement leachates

Due to their potential retention capacity, clay minerals have been proposed for use in the engineered barriers for the storage of high-level radioactive actinides in deep geological waste repositories. However, there is still a lack of data on the sorption of actinides in clays in conditions simulating those of the repositories. The present article examines the sorption of two lanthanides (actinide analogues) in a set of smectitic clays (FEBEX bentonite, MX80 bentonite, hectorite, saponite, Otay montmorillonite, and Texas montmorillonite). Distribution coefficients (K_d) were determined in two media: water and 0.02 mol L⁻¹ Ca, the latter representing the cement leachates that may modify the chemical composition of the water in contact with the clay. The K_d values of the lanthanides used in the experiments (La and Lu) varied greatly (25-50 000 L kg⁻¹) depending on the ionic medium (higher values in water than in the Ca medium), the initial lanthanide concentration (up to three orders of magnitude decrease inversely with lanthanide concentration), and the examined clay (up to one order of magnitude for the same lanthanide and sorption medium). Freundlich and Langmuir isotherms were used to fit sorption data to allow comparison of the sorption parameters among smectites. The model based on the two-site Langmuir isotherms provided the best fit of the sorption data, confirming the existence of sorption sites with different binding energies. The sites with higher sorption affinity were about 6% of the total sorption capacity in the water medium, and up to 17% in the Ca medium, although in this latter site sorption selectivity was lower. The wide range of K_d values obtained regarding the factors examined indicated that the retention properties of the clays should also be considered when selecting a suitable clay for engineered barriers.     

Clay mineral weathering and contaminant dynamics in a caustic aqueous system: I. Wet chemistry and aging effects

Caustic high level radioactive waste induces mineral weathering reactions that can influence the fate of radionuclides released in the vicinity of leaking storage tanks. The uptake and release of Cs^I and Sr^II were studied in batch reactors of 2:1 layer-type silicates—illite (Il), vermiculite (Vm) and montmorillonite (Mt)—under geochemical conditions characteristic of leaking tank waste at the Hanford Site in WA (0.05 m Al_T, 2 m Na⁺, 1 m NO₃⁻, pH ∼14, Cs and Sr present as co-contaminants). Time series (0 to 369 d) experiments were conducted at 298 K, with initial [Cs]₀ and [Sr]₀ concentrations from 10⁻⁵ to 10⁻³ mol kg⁻¹. Clay mineral type affected the rates of (i) hydroxide promoted dissolution of Si, Al and Fe, (ii) precipitation of secondary solids and (iii) uptake of Cs and Sr. Initial Si release to solution followed the order Mt > Vm > Il. An abrupt decrease in soluble Si and/or Al after 33 d for Mt and Vm systems, and after 190 d for Il suspensions was concurrent with accumulation of secondary aluminosilicate precipitates. Strontium uptake exceeded that of Cs in both rate and extent, although sorbed Cs was generally more recalcitrant to subsequent desorption and dissolution. After 369 d reaction time, reacted Il, Vm and Mt solids retained up to 17, 47 and 14 mmol kg⁻¹ (0.18, 0.24 and 0.02 μmol m⁻²) of Cs, and 0, 27 and 22 mmol kg⁻¹ (0, 0.14 and 0.03 μmol m⁻²) Sr, respectively, which were not removed in subsequent Mg exchange or oxalic acid dissolution reactions. Solubility of Al and Si decreased with initial Cs and Sr concentration in Mt and Il, but not in Vm. High co-contaminant sorption to the Vm clay, therefore, appears to diminish the influence of those ions on mineral transformation rates.     

Characterization and iodide adsorption behaviour of HDPY+ modified bentonite

Owing to its favourable physical, chemical and rheological properties, densely compacted bentonite or bentonite-sand mix is considered as a suitable buffer material in deep geological repositories to store high level nuclear waste. Iodine-129 is one of the significant nuclides in the high level waste owing to its long half life and poor sorption onto most geologic media. Bentonite by virtue of negatively charged surface has negligible affinity to retain iodide ions. As organo-bentonites are known to retain iodide ions, the present study characterizes hexadecylpyridinium chloride (HDPyCl.H₂O) treated bentonite from Barmer India (referred as HDPy⁺B) for physico-chemical properties, engineering properties and the iodide adsorption behavior of the organo clay. Batch experiments revealed that HDPy⁺ ions are largely retained (94 % retention) via cation exchange; the ion-exchange process neutralizes the negative surface charge and bridges clay particles leading to reduction in Atterberg limits, clay content and sediment volume. The organo clay retains iodide by Coulombic attraction (at primary sites) and anion exchange (at secondary sites). The free-energy change (ΔG ^o = ?25.5 kJ/mol) value indicated that iodide retention by organo clay is favored physical adsorption process. Iodide adsorption capacity of organo clay decreased significantly (85–100 %) on dilution with 50–80 % bentonite. On the other hand, dilution of bentonite with 50 % organo clay caused 58 % reduction in swell potential and 21 % reduction in swell pressure.     

Arsenic removal from aqueous solutions by mixed magnetite–maghemite nanoparticles

In this study, magnetite–maghemite nanoparticles were used to treat arsenic-contaminated water. X-ray photoelectron spectroscopy (XPS) studies showed the presence of arsenic on the surface of magnetite–maghemite nanoparticles. Theoretical multiplet analysis of the magnetite–maghemite mixture (Fe₃O₄-γFe₂O₃) reported 30.8% of maghemite and 69.2% of magnetite. The results show that redox reaction occurred on magnetite–maghemite mixture surface when arsenic was introduced. The study showed that, apart from pH, the removal of arsenic from contaminated water also depends on contact time and initial concentration of arsenic. Equilibrium was achieved in 3 h in the case of 2 mg/L of As(V) and As(III) concentrations at pH 6.5. The results further suggest that arsenic adsorption involved the formation of weak arsenic-iron oxide complexes at the magnetite–maghemite surface. In groundwater, arsenic adsorption capacity of magnetite–maghemite nanoparticles at room temperature, calculated from the Langmuir isotherm, was 80 μmol/g and Gibbs free energy (∆G⁰, kJ/mol) for arsenic removal was −35 kJ/mol, indicating the spontaneous nature of adsorption on magnetite–maghemite nanoparticles.     

ZH型重金属螯合纤维对水溶液中Sr2+的吸附行为

研究了ZH型重金属螯合纤维对水溶液中Sr~(2+)的吸附行为,考察了pH值、纤维加入量、Sr~(2+)初始浓度、作用时间等对吸附行为的影响,并采用SEM、EDS和FTIR等现代分析测试手段探讨了ZH型重金属螯合纤维对Sr~(2+)的吸附机制。结果表明,在pH值为7.0、纤维加入量为2.0 g/L、Sr~(2+)初始质量浓度为50 mg/L的条件下,纤维对Sr~(2+)的吸附在4 h左右基本达到平衡。实验条件下ZH型重金属螯合纤维对Sr~(2+)的最大吸附量可达26.22 mg/g。等温吸附拟合结果表明,ZH型重金属螯合纤维对Sr~(2+)的吸附可能是以单分子层为主的单分子层和多分子层吸附共同作用的结果。纤维对Sr~(2+)的动力学吸附过程符合准二级动力学模型。红外光谱分析表明Sr~(2+)与纤维上—NH_2和—COOH等基团进行配位络合从而吸附在纤维表面,—CH_2—和C=CH_2等基团参与此吸附过程。能谱分析表明Sr~(2+)与纤维上Na~+和Ca~(2+)还存在着离子交换作用。     

Thermodynamic properties of Pd chloride complexes and the Pd2+(aq) ion in aqueous solutions

Based on the expert review of literature data on the thermodynamic properties of species in the Cl-Pd system, stepwise and overall stability constants are recommended for species of the composition [PdCl _n ]^{2 ? n} , and the standard electrode potential of the half-cell PdCl ₄ ^2? /Pd(c) is evaluated at E _298,15° = 0.646 ± 0.007 V, which corresponds to Δ _f G _298.15° = ?400.4 ± 1.4 kJ/mol for the ion PdCl ₄ ^2? (aq). Derived from calorimetric data, Δ _f H _298.15° PdCl ₄ ^2? (aq) = ?524.6 ± 1.6 kJ/mol and Δ _f H _298.15° Pd²⁺(aq) = 189.7 ± 2.6 kJ/mol. The assumed values of the overall stability constant of the PdCl ₄ ^2? ion and the standard electrode potential of the PdCl ₄ ^2? /Pd(c) half-cell correspond to Δ _f G _298.15° = 190.1 ± 1.4 kJ/mol and S _298.15° = ?94.2 ± 10 J/(mol K) for the Pd²⁺(aq) ion.     

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

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.     

Sorption of Ni on Na-rectorite studied by batch and spectroscopy methods

Sorption of Ni²⁺ on Na-rectorite as a function of contact time, temperature, pH and fulvic acid (FA)/humic acid (HA) was studied under ambient conditions. A pseudo-second-order rate equation was used to simulate the kinetic sorption. The removal of Ni²⁺ increased with increasing pH. The presence of FA/HA enhanced the sorption of Ni²⁺ at low pH values, whereas no drastic effect of FA/HA on Ni²⁺ uptake to rectorite was found at high pH values. The diffuse layer model (DLM) fitted the experimental data of Ni²⁺ sorption in the absence and presence of FA/HA very well with the aid of FITEQL 3.2. The Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were used to simulate the sorption isotherms of Ni²⁺ at different temperatures. The thermodynamic data (ΔH⁰, ΔS⁰, ΔG⁰) were calculated from the temperature dependent sorption isotherms and the results suggested that the sorption process of Ni²⁺ on rectorite was spontaneous and endothermic. The sorption and species of Ni²⁺ on rectorite in the presence and absence of FA/HA was also investigated and characterized by XPS. The spectroscopic analysis indicated no drastic structural changes of Na-rectorite and the sorption of Ni²⁺ mainly occurred on the surface and at the edge position of Na-rectorite.     

Modelling of Cs sorption in natural mixed-clays and the effects of ion competition

Cs migration in the environment is mainly controlled by sorption onto mineral surfaces, in particular on clay minerals. With the objective of designing a geochemical reactive barrier to treat ¹³⁷Cs accidental pollution in an industrial waste repository, different natural clayrocks were studied to analyse their capacity to retain Cs.The simple semi-empiric K_d-approach for experimental data analysis, is unsatisfactory to describe the variability of sorption upon chemical changes. Indeed, due to the high salinity of the site, the effects of competitive ions must be evaluated and quantified. Thus, the development of sorption models, capable of reproducing experimental data obtained under conditions representative of the contaminated site, and applicable to reactive transport studies, is needed.In this study, a model for Cs sorption, which takes into account the main mineralogy of the sorbent, the composition of the natural water (and ion competition) was successfully applied to interpret the non-linear Cs sorption under natural conditions.The selectivity coefficients of Cs with respect to the most important cations present in the site water (Na, K, NH₄, Ca) were derived by means of experiments in single clay minerals and synthetic mono-component solutions. Then, these parameters were tested in systems of increasing complexity.Considering the mineralogical composition of raw materials, it was shown that the principal contribution to Cs sorption is given by the mineral illite, while smectite starts to be relevant only at very high Cs loadings. Kaolinite, even in concentrations around 10 wt% of the clayey fraction, played only a minor role.With respect to the solution composition, the model was able to predict Cs sorption in electrolyte concentrations up to twice than that of seawater and up to 500 mg/L NH₄⁺. The effect of highly competing ions, especially NH₄⁺ and K⁺, on Cs retention is more important at low ionic strengths and low Cs loadings, where adsorption is dominated by illite selective frayed edge sites, FES. Divalent cations are not especially relevant as competing cations for Cs.     

Impact of highly basic solutions on sorption of Cs to subsurface sediments from the Hanford site, USA

The effect of caustic NaNO₃ solutions on the sorption of ¹³⁷Cs to a Hanford site micaceous subsurface sediment was investigated as a function of base exposure time (up to 168 d), temperature (10°C or 50°C), and NaOH concentration (0.1 mol/L to 3 mol/L). At 10°C and 0.1 M NaOH, the slow evolution of [Al]_aq was in stark contrast to the rapid increase and subsequent loss of [Al]_aq observed at 50°C (regardless of base concentration). Exposure to 0.1 M NaOH at 10°C for up to 168 d exhibited little if any measurable effect on sediment mineralogy, Cs⁺ sorption, or Cs⁺ selectivity; sorption was well described with a two-site ion exchange model modified to include enthalpy effects. At 50°C, dissolution of phyllosilicate minerals increased with [OH]. A zeolite (tetranatrolite; Na₂Al₂Si₃O₁₀·2H₂O) precipitated in 0.1 M NaOH after about 7 days, while an unnamed mineral phase (Na₁₄Al₁₂Si₁₃O₅₁·6H₂O) precipitated after 4 and 2 days of exposure to 1 M and 3 M NaOH solutions, respectively. Short-term (16 h) Cs⁺ sorption isotherms (10⁻⁹-10⁻² mol/L) were measured on sediment after exposure to 0.1 M NaOH for 56, 112, and 168 days at 50°C. There was a trend toward slightly lower conditional equilibrium exchange constants (Δlog _Na^CsK_c ∼ 0.25) over the entire range of surface coverage, and a slight loss of high affinity sites (15%) after 168 days of pretreatment with 0.1 M base solution. Cs⁺ sorption to sediment over longer times was also measured at 50°C in the presence of NaOH (0.1 M, 1 M, and 3 M NaOH) at Cs⁺ concentrations selected to probe a range of adsorption densities. Model simulations of Cs⁺ sorption to the sediment in the presence of 0.1 M NaOH for 112 days slightly under-predicted sorption at the lower Cs⁺ adsorption densities. At the higher adsorption densities, model simulations under-predicted sorption by 57%. This under-prediction was surmised to be the result of tetranatrolite precipitation, and subsequent slow Na → Cs exchange. At higher OH concentrations, Cs⁺ sorption in the presence of base for 112 days was unexpectedly equal to, or greater than that expected for pristine sediment. The precipitation of secondary phases, coupled with the fairly unique mica distribution and quantity across all size-fractions in the Hanford sediment, appears to mitigate the impact of base dissolution on Cs⁺ sorption.