Thallium adsorption onto phyllosilicate minerals.

The adsorption of thallium (Tl) onto phyllosilicate minerals plays a critical role in the retention of Tl in soils and sediments and the potential transfer of Tl into plants and groundwater. Especially micaceous minerals are thought to strongly bind monovalent Tl(I), in analogy to their strong binding of Cs. To advance the understanding of Tl(I) adsorption onto phyllosilicate minerals, we studied the adsorption of Tl(I) onto Na- and K-saturated illite and Na-saturated smectite, two muscovites, two vermiculites and a naturally Tl-enriched soil clay mineral fraction. Macroscopic adsorption isotherms were combined with the characterization of the adsorbed Tl by X-ray absorption spectroscopy (XAS). In combination, the results suggest that the adsorption of Tl(I) onto phyllosilicate minerals can be interpreted in terms of three major uptake paths: (i) highest-affinity inner-sphere adsorption of dehydrated Tl+ on a very low number of adsorption sites at the wedge of frayed particle edges of illite and around collapsed zones in vermiculite interlayers through complexation between two siloxane cavities, (ii) intermediate-affinity inner-sphere adsorption of partially dehydrated Tl+ on the planar surfaces of illite and muscovite through complexation onto siloxane cavities, (iii) low-affinity adsorption of hydrated Tl+, especially in the hydrated interlayers of smectite and expanded vermiculite. At the frayed edges of illite particles and in the vermiculite interlayer, Tl uptake can lead to the formation of new wedge sites that enable further adsorption of dehydrated Tl+. On the soil clay fraction, a shift in Tl(I) uptake from frayed edge sites (on illite) to planar sites (on illite and muscovite) was observed with increasing Tl(I) loading. The results from this study show that the adsorption of Tl(I) onto phyllosilicate minerals follows the same trends as reported for Cs and Rb and thus suggests that concepts to describe the retention of (radio)cesium by different types of phyllosilicate minerals in soils, sediments and rocks are also applicable to Tl(I).

Thallium Adsorption onto Illite.

We investigated the adsorption of Tl+ onto purified Illite du Puy (IdP). Distribution coefficients (Kd) for trace Tl adsorption indicated a moderate pH-dependence from pH 2.5 to 11. Adsorption isotherms measured at Tl+ concentrations from 10-9 to 10-2 M at near-neutral pH on illite saturated with Na+ (100 mM), K+ (1 and 10 mM), NH4+ (10 mM) or Ca2+ (5 mM) revealed a high adsorption affinity of Tl+ in Na+- and Ca2+-electrolytes and strong competition with K+ and NH4+. Cation exchange selectivity coefficients for Tl+ with respect to Na+, K+, NH4+, and Ca2+ were derived using a 3-site sorption model. They confirmed the strong adsorption of Tl+ at the frayed edges of illite, with Tl selectivity coefficients between those reported for Rb+ and Cs+. X-ray absorption spectra of Tl adsorbed onto Na-exchanged IdP indicated a shift from adsorption of (dehydrated) Tl+ at the frayed edges at low loadings to adsorption of (hydrated) Tl+ on planar sites at the highest loadings. Our results suggest that illite is an important adsorbent for Tl in soils and sediments, considering its often high abundance and its stability relative to other potential adsorbents and the selective nature of Tl+ uptake by illite.

Fe(II) uptake on natural montmorillonites. II. Surface complexation modeling.

Fe(II) sorption edges and isotherms have been measured on low structural Fe-content montmorillonite (STx) and high structural Fe-content montmorillonite (SWy) under anoxic (O2 < 0.1 ppm) and strongly reducing conditions (Eh = -0.64 V). Under anoxic conditions Fe(II) sorption on SWy was significantly higher than on STx, whereas the sorption under reducing conditions was essentially the same. The uptake behavior of Fe(II) on STx under all redox conditions (Eh = +0.28 to -0.64 V) and SWy under reducing conditions (Eh = -0.64 V) was consistent with previous measurements made on other divalent transition metals. All of the sorption data could be modeled with the two-site protolysis nonelectrostatic surface complexation and cation exchange (2SPNE SC/CE) sorption model including an additional surface complexation reaction for Fe(II) which involved the surface oxidation of ferrous iron surface complexes (≡S(S,W)OFe(+)) to ferric iron surface complexes (≡S(S,W)OFe(2+)) on both the strong and weak sites. The electron acceptor sites on the montmorillonite are postulated to be the structural Fe(III).

Fe(II) uptake on natural montmorillonites. I. Macroscopic and spectroscopic characterization.

Iron is an important redox-active element that is ubiquitous in both engineered and natural environments. In this study, the retention mechanism of Fe(II) on clay minerals was investigated using macroscopic sorption experiments combined with Mössbauer and extended X-ray absorption fine structure (EXAFS) spectroscopy. Sorption edges and isotherms were measured under anoxic conditions on natural Fe-bearing montmorillonites (STx, SWy, and SWa) having different structural Fe contents ranging from 0.5 to 15.4 wt % and different initial Fe redox states. Batch experiments indicated that, in the case of low Fe-bearing (STx) and dithionite-reduced clays, the Fe(II) uptake follows the sorption behavior of other divalent transition metals, whereas Fe(II) sorption increased by up to 2 orders of magnitude on the unreduced, Fe(III)-rich montmorillonites (SWy and SWa). Mössbauer spectroscopy analysis revealed that nearly all the sorbed Fe(II) was oxidized to surface-bound Fe(III) and secondary Fe(III) precipitates were formed on the Fe(III)-rich montmorillonite, while sorbed Fe is predominantly present as Fe(II) on Fe-low and dithionite-reduced clays. The results provide compelling evidence that Fe(II) uptake characteristics on clay minerals are strongly correlated to the redox properties of the structural Fe(III). The improved understanding of the interfacial redox interactions between sorbed Fe(II) and clay minerals gained in this study is essential for future studies developing Fe(II) sorption models on natural montmorillonites.

Competitive Fe(II)-Zn(II) uptake on a synthetic montmorillonite.

The interaction of Fe(II) with clay minerals is of particular relevance in global geochemical processes controlling metal and nutrient cycles and the fate of contaminants. In this context, the influence of competitive sorption effects between Fe(II) and other relevant transition metals on their uptake characteristics and mobility remains an important issue. Macroscopic sorption experiments combined with surface complexation modeling and extended X-ray absorption fine structure (EXAFS) spectroscopy were applied to elucidate competitive sorption processes between divalent Fe and Zn at the clay mineral-water interface. Sorption isotherms were measured on a synthetic iron-free montmorillonite (IFM) under anoxic conditions (O2 <0.1 ppm) for the combinations of Zn(II)/Fe(II) and Fe(II)/Zn(II), where the former metal in each pair represents the trace metal (<10(-7) M) and the latter the competing metal at higher concentrations (10(-7) to 10(-3) M). Results of the batch sorption and EXAFS measurements indicated that Fe(II) is competing with trace Zn(II) for the same type of strong sites if Fe(II) is present in excess, whereas no competition between trace Fe(II) and Zn(II) was observed if Zn(II) is present at high concentrations. The noncompetitive behavior suggests the existence of sorption sites which have a higher affinity for Fe(III), where surface-induced oxidation of the sorbed Fe(II) to Fe(III) occurred, and which are not accessible for Zn(II). The understanding of this competitive uptake mechanism between Fe(II) and Zn(II) is of great importance to assess the bioavailability and mobility of transition metals in the natural environment.

Fe(II) sorption on a synthetic montmorillonite. A combined macroscopic and spectroscopic study.

Extended X-ray absorption fine structure (EXAFS) and Mössbauer spectroscopy combined with macroscopic sorption experiments were employed to investigate the sorption mechanism of Fe(II) on an iron-free synthetic montmorillonite (Na-IFM). Batch sorption experiments were performed to measure the Fe(II) uptake on Na-IFM at trace concentrations as a function of pH and as a function of sorbate concentration at pH 6.2 and 6.7 under anoxic conditions (O2 < 0.1 ppm). A two-site protolysis nonelectrostatic surface complexation and cation exchange sorption model was used to quantitatively describe the uptake of Fe(II) on Na-IFM. Two types of clay surface binding sites were required to model the Fe(II) sorption, the so-called strong (≡S(S)OH) and weak (≡S(W)OH) sites. EXAFS data show spectroscopic differences between Fe sorbed at low and medium absorber concentrations that were chosen to be characteristic for sorption on strong and weak sites, respectively. Data analysis indicates that Fe is located in the continuity of the octahedral sheet at trans-symmetric sites. Mössbauer spectroscopy measurements confirmed that iron sorbed on the weak edge sites is predominantly present as Fe(II), whereas a significant part of surface-bound Fe(III) was produced on the strong sites (∼12% vs ∼37% Fe(III) species to total sorbed Fe).

Redox properties of structural Fe in clay minerals. 1. Electrochemical quantification of electron-donating and -accepting capacities of smectites.

Clay minerals often contain redox-active structural iron that participates in electron transfer reactions with environmental pollutants, bacteria, and biological nutrients. Measuring the redox properties of structural Fe in clay minerals using electrochemical approaches, however, has proven to be difficult due to a lack of reactivity between clay minerals and electrodes. Here, we overcome this limitation by using one-electron-transfer mediating compounds to facilitate electron transfer between structural Fe in clay minerals and a vitreous carbon working electrode in an electrochemical cell. Using this approach, the electron-accepting and -donating capacities (Q(EAC) and Q(EDC)) were quantified at applied potentials (E(H)) of -0.60 V and +0.61 V (vs SHE), respectively, for four natural Fe-bearing smectites (i.e., SWa-1, SWy-2, NAu-1, and NAu-2) having different total Fe contents (Fe(total) = 2.3 to 21.2 wt % Fe) and varied initial Fe(2+)/Fe(total) states. For every SWa-1 and SWy-2 sample, all the structural Fe was redox-active over the tested E(H) range, demonstrating reliable quantification of Fe content and redox state. Yet for NAu-1 and NAu-2, a significant fraction of the structural Fe was redox-inactive, which was attributed to Fe-rich smectites requiring more extreme E(H)-values to achieve complete Fe reduction and/or oxidation. The Q(EAC) and Q(EDC) values provided here can be used as benchmarks in future studies examining the extent of reduction and oxidation of Fe-bearing smectites.

A spectroscopic characterization and quantification of m(III)/clay mineral outer-sphere complexes.

For the long-term safety assessment of deep radioactive waste repositories an understanding of the interactions of actinides with mineral surfaces at a molecular level is necessary. The retention/mobility of the released radionuclides is strongly dependent on sorption/desorption reactions at mineral surfaces. Thus, a quantitative understanding of the uptake mechanisms of actinides on clay minerals will make an important contribution to long-term safety assessments. Using time-resolved laser fluorescence spectroscopy (TRLFS), it was possible to differentiate between nonsorbed aquo ions and outer-sphere sorbed Cm(III) onto different montmorillonites. In addition, Cm(III)/clay outer-sphere complexation at different ionic strengths using NaCI as the background electrolyte is quantified. Finally, the results are verified by sorption model calculations.

Diffusion of 22Na and 85Sr in montmorillonite: evidence of interlayer diffusion being the dominant pathway at high compaction.

A mechanistic understanding of transport phenomena in compacted clays is essential for the use of such materials as engineered barrier systems for the safe geological disposal of radioactive wastes. The present contribution is a first step in the development of an integrative treatment of the properties of tracer cations in compacted bentonites with respect to diffusion and sorption. The diffusion of 22Na and 85Sr in highly compacted montmorillonite and kaolinite is investigated as a function of the "external salt concentration" (NaClO4), i.e., of the solution in equilibrium with the clay. Consistent results were obtained from through-diffusion experiments and tracer profile analysis. Knowledge of genuine diffusion coefficients of the filter plates turned out to be crucial in cases where the diffusive resistance of the filter plates was similar to that of the clay. Diffusion coefficients formally calculated on the basis of the tracer concentration gradient in the external aqueous phase, and the sorption distribution ratios were found to decrease with increasing external salt concentration in the case of montmorillonite. In a logarithmic representation of these data, a slope of -1 was obtained for the monovalent 22Na, whereas the slope was -2 for the divalent 85Sr. In the case of kaolinite, diffusion coefficients were independent of the external salt concentration. It is postulated that the diffusion of the tracer cation through the interlayer water is the dominant pathway in compacted swelling clays under the experimental conditions tested. Effective diffusion coefficients, based on a tracer concentration gradient in the interlayer water of the clay, were found to be independent of the composition of the external aqueous phase. The latter gradient is assumed to be a function of the external salt concentration, according to a calculated distribution of the tracer cation between free pore water and the interlayer water via cation exchange.

Porewater chemistry in compacted re-saturated MX-80 bentonite.

Bentonites of various types are being investigated in many countries as backfill materials in high-level radioactive waste disposal concepts. Being able to understand the chemistry of the porewater in compacted bentonite is very important since it is critical to predicting radionuclide solubilities and to the synthesis of sorption data bases, and hence to repository safety studies. In this paper, porewater compositions in compacted bentonites are calculated, taking into consideration such factors as montmorillonite swelling, semi-permeable membrane effects, very low "free water" volumes, and the highly effective buffering characteristics of the exchangeable cations and the amphoteric edge sites. The former buffer the cation concentrations and the latter fix the pH in the porewater of a re-saturated bentonite. The above considerations are used in conjunction with previously measured physico-chemical characterisation data on MX-80 powder to calculate porewater compositions in compacted bentonites. For the MX-80 material specified, the porewaters calculated for initial dry densities between 1200 and 1600 kg m(-3) had relatively high ionic strengths (I approximately 0.3 M), similar cation concentrations and a pH equal to 8.0. The porewaters changed from being Na(2)SO(4)-rich at 1200 kg m(-3) to a NaCl/Na(2)SO(4) type water at 1600 kg m(-3).

Th uptake on montmorillonite: a powder and polarized extended X-ray absorption fine structure (EXAFS) study.

The uptake process of Th(IV) onto montmorillonite was studied using powder and polarized-EXAFS (P-EXAFS) spectroscopy. Sorption samples were prepared in 0.1 M NaClO(4) solutions either undersaturated (pH 2 and 3, [Th](initial): 2.7x10(-6) to 4x10(-4) M) or supersatured (pH 5, [Th](initial): 4.3x10(-5) to 4x10(-4) M) with respect to amorphous ThO(2). Th loading varied between 1-157 micromol/g at pH 3 and 14-166 micromol/g at pH 5 and equaled 41 micromol/g at pH 2. At pH 5 and high surface loading the EXAFS spectrum resembled that of amorphous Th(OH)(4), suggesting the precipitation of a Th hydrous hydroxide. At low and intermediate surface coverage two O coordination shells at approximately 2.24 and approximately 2.48 A, and one Si shell at 3.81-3.88 A, were systematically observed regardless of pH. The formation of Th nucleation products and Th-Si solution complexes and the sorption of Th on a silica precipitate were excluded from the EXAFS spectra analysis and solution chemistry. In these conditions, Th was shown to bond the montmorillonite surface by sharing double corners with Si tetrahedra. This structural interpretation is consistent with surface coverage calculations which showed that the edge sites were saturated in the two highest concentrated samples (34 and 157 micromol/g) at pH 3.