An X-ray absorption spectroscopy study of the structure and reversibility of copper adsorbed to montmorillonite clay

X-ray absorption spectroscopy (XAS) and adsorption-desorption measurements have been performed to assess the relationship between the structure and reversibility of copper complexes on montmorillonite clay. By varying the solution pH and background electrolyte concentration, the adsorption of copper on either the edge sites or permanent charge sites of montmorillonite was controlled. This allowed the structure and reversibility of copper complexes on each of these site types to be assessed independently of each other. XAS analysis of copper adsorbed on the permanent charge sites indicated outer-sphere surface complexes, with these complexes showing sorption reversibility. For copper complexes formed on the edge sites of montmorillonite, XAS data confirmed the presence of monomer and dimer copper surface complexes. Sorption irreversibility at edge sites was noted at copper coverages less than 20 μmoles/g clay at pH=4.2 and at coverages greater than 50 μmoles/g clay at pH=6.8. At pH=6.8, higher Cu-Cu coordination numbers indicated the copper sorption irreversibility may be due, in part, to the formation of dimer surface complexes. The coordination numbers at pH=4.2 indicated the irreversibility could be due to the formation of dimers or due to formation of surface complexes on high energy edge sites.     

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.     

Macroscopic and spectroscopic analysis of lanthanide adsorption to bacterial cells

This study was designed to combine surface complexation modelling of macroscopic adsorption data with X-ray Absorption Spectroscopic (XAS) measurements to identify lanthanide sorption sites on the bacterial surface. The adsorption of selected representatives for light (La and Nd), middle (Sm and Gd) and heavy (Er and Yb) lanthanides was measured as a function of pH, and biomass samples exposed to 4 mg/L lanthanide at pH 3.5 and 6 were analysed using XAS. Surface complexation modelling was consistent with the light lanthanides adsorbing to phosphate sites, whereas the adsorption of middle and heavy lanthanides could be modelled equally well by carboxyl and phosphate sites. The existence of such mixed mode coordination was confirmed by Extended X-ray Absorption Fine Structure (EXAFS) analysis, which was also consistent with adsorption to phosphate sites at low pH, with secondary involvement of carboxyl sites at high adsorption density (high pH). Thus, the two approaches yield broadly consistent information with regard to surface site identity and lanthanide coordination environment. Furthermore, spectroscopic analysis suggests that coordination to phosphate sites is monodentate at the metal/biomass ratios used. Based on the best-fitting pK_a site, we infer that the phosphate sites are located on N-acetylglucosamine phosphate, the most likely polymer on gram-negative cells with potential phosphate sites that deprotonate around neutral pH.     

Physical protection of lignin by organic matter and clay minerals from chemical oxidation

The role of organic matter (OM) concentration, structure and composition and how these relate to mineral protection is important for the understanding of long term soil OM dynamics. Various OM–clay complexes were constructed by sequential sorption of lignin and dodecanoic acid to montmorillonite. Humic acid–montmorillonite complexes were prepared at pH 4 and 7 to vary OM conformation prior to sorption. Results obtained with constructed OM–clay complexes were tested with isolated mineral fractions from two soils. Oxidation with an acidic NaClO₂ solution was used to chemically oxidize lignin in the OM–clay complexes, sand-, silt- and clay-size soil fractions to test whether or not it can be protected from chemical attack. Gas chromatography–mass spectrometry was used to analyze lignin-derived phenols, cutin OH–acid (after CuO oxidation), fatty acid and n-alkanol concentrations and composition. We found that carbon content was not solely responsible for lignin stability against chemical oxidation. Lignin was protected from chemical oxidation through coating with dodecanoic acid and sorption of humic acid to clay minerals in a stretched conformation at pH 7. Therefore, interactions between OM constituents as well as OM conformation are important factors that protect lignin from chemical oxidation. Lignin-derived phenol dimers in the Grassland-Forest Transition soil fractions were protected from chemical oxidation to a greater extent compared to those in Grassland soil fractions. Therefore, although lignin was protected from degradation through mineral association, the extent of this protection was also related to OM content and the specific stability of lignin components.     

Sorption of lanthanides on smectite and kaolinite

Experiments were carried out to investigate the sorption of the complete lanthanide series (Ln or rare earth elements, REE) on a kaolinite and an a Na-montmorillonite at 22°C over a wide range of pH (3-9). Experiments were conducted at two ionic strengths, 0.025 and 0.5 M, using two different background electrolytes (NaNO₃ or NaClO₄) under atmospheric conditions or N₂ flow (glove box). The REE sorption does not depend on the background electrolyte or the presence of dissolved CO₂, but is controlled by the nature of the clay minerals, the pH and the ionic strength. At 0.5 M, both clay minerals exhibit the same pH dependence for the Ln sorption edge, with a large increase in the sorption coefficient (K_D) above pH 5.5. At 0.025 M, the measured K_D is influenced by the Cation Exchange Capacity (CEC) of the minerals. Two different behaviours are observed for smectite: between pH 3 and 6, the K_D is weakly pH-dependent, while above pH 6, there is a slight decrease in log K_D. This can be explained by a particular arrangement of the particles. For kaolinite, the sorption coefficient exhibits a linear increase with increasing pH over the studied pH range. A fractionation is observed that due to the selective sorption between the HREEs and the LREEs at high ionic strength, the heavy REE is being more sorbed than the light REE. These results can be interpreted in terms of the surface chemistry of clay minerals, where two types of surface charge are able to coexist: the permanent structural charge and the variable pH-dependent charge. The fractionation due to sorption observed at high ionic strength can be interpreted either because of a competition with sodium or because of the formation of inner-sphere complexes. Both processes could favour the sorption of HREEs according to the lanthanide contraction.     

Crystal chemistry of clay-Mn oxide associations in soils, fractures, and matrix of the Bandelier Tuff, Pajarito Mesa, New Mexico

The upper 25 m of Bandelier Tuff at Pajarito Mesa, New Mexico, include soils, shallow fractures, deeper fractures, and tuff matrices in which clays provide a record of transport and alteration. The principal pathways within this system are fractures that penetrate the tuff. Large fractures that host deep root penetration provide a setting in which clay deposits accumulate through particulate or colloidal migration from the soil zone. Clays throughout the system are predominantly expandable interstratified illite/smectites (I/S), but clays of the tuff matrix at depth are distinctly Fe-rich and are not mixed with clays transported from the surface into fractures. Chemical alteration superimposed on clay particles transported into fractures results in clays with lower Al : Si ratios, higher Na, and higher lanthanide content with increasingly negative Eu anomalies with depth. These changes are accompanied by invasion and precipitation of Mn oxides, principally birnessite, within clay bodies. Investigation of the Mn oxides by synchrotron X-ray fluorescence (SXRF) shows that Mn is associated with Ba, Ce, Ni, and Pb. In addition, synchrotron X-ray absorption near-edge structure (XANES) spectra show that Ce in Mn oxides occurs as Ce³⁺ and Ce⁴⁺, with average Ce oxidation state of ∼3.75. The Mn oxides intergrown with clays actively participate in removal of Ce from solution, accompanied by oxidation of Ce³⁺ to Ce⁴⁺. Other lanthanides are accumulated by the clays but are not concentrated along with Ce in the Mn oxides. Extraction of Ce from solution by Mn oxides is more effective than lanthanide accumulation in clay, a process that is variable and likely influenced by defects, extent of recrystallization, and particle sizes. This dichotomy in lanthanide interaction results in locally constant Ce content but either negative or positive Ce anomalies in the clay-Mn oxide system as a consequence of variability in the abundance of the other lanthanides. Nevertheless, the net lanthanide pattern for the sum of all clay-Mn oxide samples in either shallow or deep fractures has no Ce anomaly, indicating that other lanthanides segregated from Ce are not transported beyond the range of either the shallow or deep fracture systems. Evidence from Eu anomalies indicates that lanthanides accumulated in the fracture clays are acquired from the local tuff. The clay-Mn oxide assemblage is more effective than clay alone in accumulating of a wide variety of heavy metals.     

Boron isotopic fractionation related to boron sorption on humic acid and the structure of surface complexes formed

Boron isotopic fractionation during adsorption onto Ca-flocculated Aldrich humic acid (HA) has been investigated experimentally as a function of solution pH at 25°C and I = 0.15 M. Boron aqueous concentration and isotopic composition were determined by Cs₂BO₂⁺ Positive Thermal Ionization Mass Spectrometry analysis, while the structure of B surface complexes on HA was characterized using ¹¹B Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR). Significant B sorption on HA was observed at 6 < pH < 12 with a maximum value of Kd, the partition coefficient between adsorbed and aqueous boron, equal to 40 at pH = 9.5-10. Combined ¹¹B MAS NMR analysis and FITEQL modeling of B sorption on HA showed that this element forms tetrahedrally coordinated five- or six-membered ring chelates, most likely 1,2-diol and 1,3-diol complexes at alkaline pH (8 < pH < 11) and dicarboxylic complexes at near neutral conditions (6 < pH < 9). Results of this study demonstrate for the first time that boron sorption on HA induces a strong pH-dependent isotope fractionation—with ¹¹B depleted at the surface of HA—that reaches a maximum at 5 < pH < 9 (α = 0.975, Δ = −25‰) and decreases sharply at pH >9. The measured isotope fractionation cannot be modeled assuming that the isotopic composition of the sorbed borate species is identical to that of B(OH)₄^- species in the parent solution. It is shown that the extent of isotopic fractionation depends not only on B aqueous speciation but also on the distribution and structure of the borate surface complexes formed. In agreement with energetic constrains, calculation of the isotope fractionation factors between aqueous boric acid and boron surface complexes suggests that the formation of the strained six-membered ring 1,3-diol complex yields a much higher fractionation (α_BLP1−III = 0.954-0.960, Δ = −41/-47‰) than that of the very stable five-membered ring 1,2-diol (α_BLP2−III = 0.983, Δ = −18‰). The results of this study open new perspectives to understand and model boron biogeochemical cycle. It is predicted that boron sorption onto organic matter can have important consequences for the boron isotopic composition of surface water reservoirs (seawater, groundwater, soil waters) in which either abundant organic surfaces or significant boron concentrations are available. In addition, the large isotope fractionation between aqueous boric acid and surface boron-organic complexes found in the present work makes boron a promising tracer of biologic activity.     

A surface complexation and ion exchange model of Pb and Cd competitive sorption on natural soils

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.     

Wastewater dephosphorization using crude clays

The present work aims to establish the possibility of using local clays to treat wastewater. Thus, three clay samples extracted from two localities in the south of Côte d’Ivoire have been studied in their crude state. The qualitative physicochemical study that consisted in measurement of pH variation and argillaceous particles zeta potential showed that the Nieki-Agneby clay and the Beige Anyama clay presented disposal to uptake phosphate ions in solution at pH 5. For each clay, it is shown that the tension accompanying the sorption of a phosphate ion could be estimated to ?5 mV. Differences in their composition and in the number of hydrating molecules of water were also accessible. The quantitative study performed with the Nieki-Agneby clay thereafter consisted following the sorption kinetic. The adsorption was found to reach the maximum after 5 h. of exchange, and almost 400 μg phosphate ions in per gram of clay were fixed. Future studies will focus on the modification of these materials in order to increase their sorption capacity.     

Sorption of silica by clay minerals

Clay minerals were reacted with silica-spiked solutions of unbuffered distilled water; water buffered at pH 5.5, 8 and 10; alkali chloride solutions; natural and artificial sea water to assess the influence of pH, silica and cation activities. The data are plotted as silica produced by dissolution or sorption of silica by clay surface as a function of initial silica concentration at a given pH and solution composition. This allows the determination of the dissolved silica value at which the clay mineral surface neither dissolves nor sorbs silica. The values of the various activities in different solutions are used to infer the phase equilibria between solution, clay mineral and the surface phase produced either by dissolution or sorption. Most intensively investigated were sorption reactions of kaolinite in sea water and other ionic solutions to form silica-rich, cation-rich surface phases in cationic solutions and silica-rich phases in cation-free solutions.Inferred equilibrium constants imply that silicate reconstitution is doubtful as a mechanism for partial control of silica and cation composition of sea water but is reasonable in silica-rich interstitial waters.     

The use of lanthanides for the reconstruction of Phanerozoic and Proterozoic sedimentation environments exemplified by sections in the cover and basement of the East European platform

Criteria were established for the estimation of the lanthanide composition of sedimentary complexes for the reconstruction of sedimentation conditions. The distribution of lanthanides was investigated in phosphorites and sedimentary rocks from the cover of the East European platform, and published data on the geochemistry of phosphorites from Eurasia were analyzed. Indicator lanthanide ratios were established for the determination of the climate and depth of sedimentation, and the possibility of the use of rare earth elements for the facies settings and transgression-regression cycles of sedimentation was demonstrated. The sedimentation conditions of the iron formations of the Proterozoic Kursk and Krivoi Rog sedimentary groups were inferred from the distribution of lanthanides: the hematite and magnetite quartzites are the deepest water complexes of the sedimentation profile; the climatic conditions of sedimentation were estimated as humid for shale subformations and humid-semihumid for iron formations; the depths of sedimentation in the Kursk basin was 50−300 m; the sources of iron were the material of weathering profiles and endogenous influx.     

X-ray absorption spectroscopy investigation of aqueous Co(II) and Sr(II) sorption at clay–water interfaces

Sorption processes typically control trace metal concentrations in aquatic systems. To illustrate the impact of various types of surface sites on metal ion sorption behavior, Co(II) and Sr(II) sorption by several clay minerals under a range pH and background electrolyte conditions was studied. X-ray absorption spectroscopy (XAS) was used to characterize the surface complexes formed to explain the basis for the sorption trends. At low pH, Co(II) could be displaced from the surface by increasing the Na ion concentration. XAS analysis of these samples showed that sorbed Co(II) retained the coordination structure of aqueous phase Co(II), suggesting the formation of weakly associated, outer-sphere, mononuclear Co complexes at permanent charge sites. At high pH, sorbed Co could not be displaced by increasing the Na ion concentration. The XAS analyses of these samples indicated the formation of Co coprecipitates. The results of the Sr(II) sorption experiments suggested weaker bonding between sorbed Sr and the solid surfaces, regardless of solution conditions and adsorbent. XAS analysis of Sr sorption samples revealed the formation of mononuclear, outer-sphere complexes of Sr at clay–water interfaces, similar to the outer-sphere Co sorption samples observed only at low pH.     

Oxytetracycline sorption onto Iraqi montmorillonite

This paper assesses the use of certified Iraqi montmorillonite clay as a potential sorbent for the removal of oxytetracycline (OTC) from aqueous solutions. The clay is characterized by a cation exchange capacity of 0.756 meq g^?1 and a zero point charge at pH 8.7. Aqueous solutions of OTC were equilibrated with montmorillonite under various experimental conditions, such as OTC concentration, pH and clay content, for 24 h at fixed ionic strength. Two forms of montmorillonite were evaluated: regular and iron-modified form. The effect of pH was minor on OTC adsorption. Kinetic study revealed that the sorption follows a pseudo-second-order model. Sorption isotherm showed a good fit with the Freundlich model. OTC sorption onto Fe-saturated montmorillonite was analyzed statistically using a response surface design to study the effects of experimental conditions. The introduction of iron improved the adsorption characteristics of the clay due to the ability of ferric ions to make stable complexes with OTC. The most favorable operating conditions for the treatment were deemed as follows: clay content, 6.85 g L^?1, oxytetracycline concentration, 1.0 mmol L^?1 and pH, 5.5 for the iron-modified form.     

Sorption of uranium(VI) at the clay mineral–water interface

Batch experiments were conducted to study the sorption of uranium on selected clay minerals (KGa-1b and KGa-2 reference kaolinite, SWy-2 and STx-1b reference montmorillonite, and IBECO natural bentonite) as a function of pH (4–9) and 0.001, 0.01, and 0.025 M NaCl in equilibrium with the CO₂ partial pressure of the atmosphere. Uranium concentrations were kept below 100 μg L⁻¹ to avoid precipitation of amorphous Uranium-hydroxides. Solely PTFE containers and materials were used, because experiments showed significant sorption at higher pH on glass ware. All batch experiments were performed over a period of 24 h, since kinetic experiments proved that the common 10 or 15 min are in many cases by far not sufficient to reach equilibrium. Kaolinite showed much greater uranium sorption than the other clay minerals due to the more aluminol sites available. Sorption on the poorly crystallized KGa-2 was higher than on the well-crystallized KGa-1b. Uranium sorption on STx-1b and IBECO exhibited parabolic behavior with a sorption maximum around pH 6.5. Sorption of uranium on montmorillonites showed a distinct dependency on sodium concentrations because of the effective competition between uranyl and sodium ions, whereas less significant differences in sorption were found for kaolinite. The presence of anatase as impurity in kaolinite enhanced the binding of uranyl-carbonate complexes with surface sites. The kinetic of uranium sorption behavior was primarily dependent on the clay minerals and pH. A multisite surface complexation model without assuming exchange is based on the binding of the most dominant uranium species to aluminol and silanol edge sites of montmorillonite, respectively to aluminol and titanol surface sites of kaolinite. For eight surface species, the log_k was determined from the experimental data using the parameter estimation code PEST together with PHREEQC.     

Uranyl adsorption onto montmorillonite: Evaluation of binding sites and carbonate complexation

The fate and transport of uranium in contaminated soils and sediments may be affected by adsorption onto the surface of minerals such as montmorillonite. Extended X-ray absorption fine structure (EXAFS) spectroscopy has been used to investigate the adsorption of uranyl (UO₂²⁺) onto Wyoming montmorillonite. At low pH (∼4) and low ionic strength (10⁻³ M), uranyl has an EXAFS spectrum indistinguishable from the aqueous uranyl cation, indicating binding via cation exchange. At near-neutral pH (∼7) and high ionic strength (1 M), the equatorial oxygen shell of uranyl is split, indicating inner-sphere binding to edge sites. Linear-combination fitting of the spectra of samples reacted under conditions where both types of binding are possible reveals that cation exchange at low ionic strengths on SWy-2 may be more important than predicted by past surface complexation models of U(VI) adsorption on related montmorillonites. Analysis of the binding site on the edges of montmorillonite suggests that U(VI) sorbs preferentially to [Fe(O,OH)₆] octahedral sites over [Al(O,OH)₆] sites. When bound to edge sites, U(VI) occurs as uranyl-carbonato ternary surface complexes in systems equilibrated with atmospheric CO₂. Polymeric surface complexes were not observed under any of the conditions studied. Current surface complexation models of uranyl sorption on clay minerals may need to be reevaluated to account for the possible increased importance of cation exchange reactions at low ionic strengths, the presence of reactive octahedral iron surface sites, and the formation of uranyl-carbonato ternary surface complexes. Considering the adsorption mechanisms observed in this study, future studies of U(VI) transport in the environment should consider how uranium retardation will be affected by changes in key solution parameters, such as pH, ionic strength, exchangeable cation composition, and the presence or absence of CO₂.     

Sequestration of arsenate from aqueous solution using 2-line ferrihydrite: equilibria,kinetics, and X-ray absorption spectroscopic analysis

Arsenic(V), as the arsenate (AsO₄ ^3?) ion and its conjugate acids, has a strong affinity on Fe, Mn, and Al (oxyhydr)oxides and clay minerals. Removal of arsenate from aqueous solution by poorly crystalline ferrihydrite (hydrous ferric oxide) via a combination of macroscopic (equilibria and kinetics of sorption) and X-ray absorption spectroscopic studies was investigated. The removal of arsenate significantly decreased with increasing pH and sorption maxima of approximately 1.994 mmol/g (0.192 mol_As/mol_Fe) were achieved at pH 2.0. The Langmuir isotherm is most appropriate for arsenate sorption over the wide range of pH, indicating that arsenate sorption preferentially takes place at relatively homogenous and monolayer sites rather than heterogeneous and multilayer surfaces. The kinetic study demonstrated that arsenate sorption onto 2-line ferrihydrite is considerably fast, and sorption equilibrium was achieved within the reaction time of 2 h. X-ray absorption near-edge structure spectroscopy indicates no change in oxidation state of arsenate following interaction with the ferrihydrite surfaces. Extended X-ray absorption fine structure spectroscopy supports the efficient removal of arsenate by the 2-line ferrihydrite through the formation of highly stable inner-sphere surface complexes, such as bidentate binuclear corner-sharing (²C) and bidentate mononuclear edge-sharing (²E) complexes.     

Interaction of fluoride with hydroxyaluminum-montmorillonite complexes and implications for fluoride-contaminated acidic soils

In acidic soils and aquatic environments, polymeric hydroxyaluminum (HyAl) cations with various OH/Al ratios are ubiquitous. Hydroxyaluminum-montmorillonite (HyAl-Mt) complexes are widely distributed in acidic to slightly acidic soils and aquatic environments. The fixation of HyAl cations on Mt can significantly modify the mineralogical and electrochemical properties of the host clay, thereby substantially influencing adsorption/desorption and transport of many nutrients and pollutants. In the present study, HyAl-Mt complexes were synthesized through adsorption of polymeric HyAl cations with OH/Al ratio of 1.6 on Na-saturated Mt (Na-Mt). Interaction of F⁻ with HyAl-Mt was investigated in acidic conditions and the environmental implications for F⁻-contaminated soils were also addressed. Results indicated that the effects of pH on F⁻ sorption by HyAl-Mt were slight in the pH range of 5.0–9.0, whereas sorption increased rapidly with decreasing pH when pH was below 4.5. At initial pH >4.0, ligand exchange was the main mechanism for F⁻ sorption. At initial pH 3.02 and high initial F⁻ concentrations, several synergic mechanisms, such as coprecipitation, scavenging and surface adsorption were involved in F⁻ removal from solution, which resulted in an abrupt and discontinuous increase in sorption capacity of HyAl-Mt for F⁻ with increasing initial F⁻ concentration, and a slight dependency of F⁻ sorption on HyAl-Mt dosage. Compared with Na-Mt, sorption capacities of HyAl-Mt for F⁻ were significantly enhanced by interlayering and coating with polymeric HyAl cations. HyAl-Mt would be important natural scavengers for F⁻. The presence of HyAl-Mt in acidic soils could greatly retard F⁻ transport and bioavailability in soil environments. Interaction of F⁻ with HyAl-Mt may mitigate acidification of F⁻-contaminated acidic soils. Application of synthetic HyAl-Mt may be one alternative for remediation of acidic F⁻-contaminated soils.     

B NMR investigation of boron interaction with mineral surfaces: Results for boehmite, silica gel and illite

Boron is an important micronutrient for plants but is toxic at high pore solution concentrations. Its mobility and migration in many geochemical environments is often controlled by reactions with mineral surfaces, and thus its speciation on mineral surfaces has been extensively investigated. Most previous studies have used IR spectroscopy to characterize the surface B-environments. We present here the first ¹¹B MAS NMR study of surface sorbed boron on minerals. The results demonstrate the capability of this method to effectively probe the local structure of the sorption sites at total B-concentrations in the samples as small as 0.03 wt% and to provide insight into the mechanisms of sorption. Signal is readily resolved for both trigonal (B(3)) and tetrahedral (B(4)) boron exchanged onto boehmite, silica gel and illite, and the resonances are readily assigned on the basis of chemical shift and quadrupole coupling constant. Boron surface densities on illite are approximately order of magnitude greater than on silica gel or boehmite. For boehmite, both B(3) and B(4) occur dominantly as inner-sphere complexes formed by ligand exchange reaction with surface aluminol sites. The B(3)/[B(3) + B(4)] ratio of approximately 0.87 does not vary significantly with pH from 3 to 11, with solution B-concentration, or with washing. The occurrence of B(3) and B(4) as inner-sphere complexes is in agreement with previous suggestions from IR studies of B-sorption on iron hydroxide, allophone, kaolinite, and hydrous ferric oxide. For silica gel, B(3) and B(4) occur principally as outer-sphere complexes or as residual precipitate from un-removed solution. The B(3)/B(4) ratio decreases with increasing pH paralleling the speciation in solution, but the relative abundance of B(4) is greater than in solution. A small fraction of the B(4) occurs as inner-sphere complexes with B(4)-O-Si linkages formed by ligand exchange reaction with silanol sites. For illite, surface boron occurs as outer-sphere B(3) and B(4), as for silica gel, and as inner-sphere B(3) and B(4), as for boehmite. Outer-sphere B(3) and B(4) are dominant at pH 3 and 5, whereas inner-sphere B(3) and B(4) are dominant at pH 9 and 11. The inner-sphere complexes probably form dominantly by ligand exchange reactions involving sites on the broken edges of illite layers.     

Experimental sorption of Ni, Cs and Ln onto a montmorillonite up to 150°C

The effect of temperature on the sorption of cations onto a dioctahedral smectite was investigated by running batch experiments at 25, 40, 80 and 150°C. We measured the distribution coefficient (Kd) of Cs⁺, Ni²⁺ and 14 lanthanides (Ln³⁺) between solutions and the montmorillonite fraction of the MX80 bentonite at various pH and ionic strengths. Up to 80°C we used a conventional experimental protocol derived from Coppin et al. (2002). At 150°C, the experiments were conducted in a PTFE reactor equipped with an internal filter allowing the sampling of clear aliquots of solution.The results show a weak but measurable influence of the temperature on the elements sorption. Kd’s for Ni²⁺ and Ln³⁺ increase by a factor 2 to 5 whereas temperature raises from 25 to 150°C. This effect seems higher at high ionic strength. The estimated apparent endothermic sorption enthalpies are 33 ± 10 kJ.mol⁻¹ and 39 ± 15 kJ.mol⁻¹ for Ni²⁺ and Eu³⁺, respectively. On the other hand, the temperature effect on Cs⁺ sorption is only evidenced at low ionic strength and under neutral conditions where the Kd decreases by a factor 3 between 25 and 150°C. Apparent exothermic sorption enthalpy for Cs⁺ on the montmorillonite is −19 ± 5 kJ.mol⁻¹.Experiments conducted at the four temperatures with the coexistence of all of the cations in the reacting solution (100 ppb of each element in the starting solution) or only one of them, produced similar values of Kd. This suggests the absence of competition between the sorbed cations, and consequently a low degree of saturation of the available sites. A fractionation of the lanthanides spectrum is also observed at high pH and high ionic strength whatever the temperature.The conclusion of this study is that the temperature dependence on sorption reflects, as the fractionation of REE or the pH and ionic strength effects, the chemical process which controls the overall reaction. In the case of an exchange dominated reaction (low pH and low ionic strength), the temperature effect is negligible. In the case of surface complexation (high pH and high ionic strength), the observed increase of Kd with temperature reflects either an increase of the sorption equilibrium constant with temperature or an endothermic property for reactions describing the montmorillonite surface chemistry.     

A model for trace metal sorption processes at the calcite surface: Adsorption of Cd2+ and subsequent solid solution formation

The rate of Cd²⁺ sorption by calcite was determined as a function of pH and Mg²⁺ in aqueous solutions saturated with respect to calcite but undersaturated with respect to CdCO₃. The sorption is characterized by two reaction steps, with the first reaching completion within 24 hours. The second step proceeded at a slow and nearly constant rate for at least 7 days. The rate of calcite recrystallization was also studied, using a Ca²⁺ isotopic exchange technique. Both the recrystallization rate of calcite and the rate of slow Cd²⁺ sorption decrease with increasing pH or with increasing Mg²⁺. The recrystallization rate could be predicted from the number of moles of Ca present in the hydrated surface layer.A model is presented which is consistent with the rates of Cd²⁺ sorption and Ca²⁺ isotopic exchange. In the model, the first step in Cd²⁺ sorption involves a fast adsorption reaction that is followed by diffusion of Cd²⁺ into a surface layer of hydrated CaCO₃ that overlies crystalline calcite. Desorption of Cd²⁺ from the hydrated layer is slow. The second step is solid solution formation in new crystalline material, which grows from the disordered mixture of Cd and Ca carbonate in the hydrated surface layer. Calculated distribution coefficients for solid solutions formed at the surface are slightly greater than the ratio of equilibrium constants for dissolution of calcite and CdCO₃, which is the value that would be expected for an ideal solid solution in equilibrium with the aqueous solution.