Rainer Dähn

Structural evidence for the sorption of Ni(II) atoms on the edges of montmorillonite clay minerals: A polarized X-ray absorption fine structure study

The nature of surface complexes formed on Ni uptake onto montmorillonite (a dioctahedral smectite) has been investigated over an extended time period by polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy. Self-supporting films of Ni-sorbed montmorillonite were prepared by contacting Ni and montmorillonite at pH 7.2, high ionic strength (0.3 M NaClO4), and low Ni concentration ([Ni]initial = 19.9 μM) for 14- and 360-d reaction time. The resulting Ni concentration on the clay varied from 4 to 7 μmol/g. Quantitative texture analysis indicates that the montmorillonite particles were well orientated with respect to the plane of the film. The full width at half maximum of the orientation distribution of the c* axes of individual clay platelets about the normal to the film plane was 44.3° (14-d reaction time) and 47.1° (360-d reaction time). These values were used to correct the coordination numbers determined by P-EXAFS for texture effects. Ni K-edge P-EXAFS spectra were recorded at angles between the incident beam and the film normal equal to 10, 35, 55, and 80°. Spectral analysis led to the identification of three nearest cationic subshells containing 2.0 ± 0.5 Al at 3.0 A and 2.0 ± 0.5 Si at 3.12 A and 4.0 ± 0.5 Si at 3.26 A. These distances are characteristic of edge-sharing linkages between Al and Ni octahedra and of corner-sharing linkages between Ni octahedra and Si tetrahedra, as in clay structures. The angular dependence of the Ni-Al and Ni-Si contributions indicates that Ni-Al pairs are oriented parallel to the film plane, whereas Ni-Si pairs are not. The study reveals the formation of Ni inner-sphere mononuclear surface complexes located at the edges of montmorillonite platelets and thus that heavy metals binding to edge sites is a possible sorption mechanism for dioctahedral smectites. Data analysis further suggests that either the number of neighboring Al atoms slightly increases from 1.6 to 2 or that the structural order of the observed surface complexes increases from 0.01 A2 to 0.005 A2 with increasing reaction time. On the basis of the low Ni-Al coordination numbers, it appears that over an extended reaction time period of 1 yr the diffusion of Ni atoms in the octahedral layer is not the major uptake mechanism of Ni onto montmorillonite.

Neoformation of Ni phyllosilicate upon Ni uptake on montmorillonite: A kinetics study by powder and polarized extended X-ray absorption fine structure spectroscopy

Abstract Wet chemistry kinetics and powder and polarized extended X-ray absorption fine structure (EXAFS and P-EXAFS) spectroscopy were combined to investigate the mechanism of Ni uptake on montmorillonite, at pH 8, high ionic strength (0.2 M Ca(NO3)2), initial Ni concentration of 660 μM, and solid concentration of 5.3 g/L. Approximately 20% of Ni sorbed within the first 24 h; thereafter, the Ni uptake rate slowed, and 12% of the initial Ni concentration remained in solution after 206 d of reaction time. Powder EXAFS spectra collected on wet pastes at 1, 14, 90, and 206 d showed the presence of Ni-Ni pairs at ∼3.08 A in an amount that gradually increased with time. Results were interpreted by the nucleation of a Ni phase having either an α-Ni-hydroxide– or a Ni-phyllosilicate–like local structure. The latter possibility was confirmed by recording P-EXAFS spectra of a highly textured, self-supporting montmorillonite film prepared in the same conditions as the wet samples and equilibrated for 14 d. The orientation distribution of the c*-axes of individual clay particles off the film plane, as measured by quantitative texture analysis, was 32.8° full width at half maximum, and this value was used to correct from texture effect the effective numbers of Ni and Si nearest neighbors determined by P-EXAFS. Ni atoms were found to be surrounded by 2.6 ± 0.5 Ni atoms at 3.08 A in the in-plane direction and by 4.2 ± 0.5 Si atoms at 3.26 A in the out-of-plane direction. These structural parameters, but also the orientation and angular dependence of the Ni and Si shells, strongly support the formation of a Ni phyllosilicate having its layers parallel to the montmorillonite layers. The neoformation of a phyllosilicate on metal uptake on montmorillonite, documented herein for the first time, has important geochemical implications because this dioctahedral smectite is overwhelmingly present in the environment. The resulting sequestration of sorbed trace metals in sparingly soluble phyllosilicate structure may durably decrease their migration and bioavailability at the Earth’s surface and near surface.

Zinc adsorption on clays inferred from atomistic simulations and EXAFS spectroscopy.

Clay minerals are efficient sinks for heavy metals in the geosphere. Knowing the uptake mechanism of these elements on clays can help to protect the natural environment from industrial pollution. In this study ab initio molecular dynamics (MD) calculations were applied to simulate the uptake of Zn on the edge surfaces of montmorillonite, a dioctahedral clay, and to explain the measured K-edge extended X-ray absorption fine structure (EXAFS) spectra of adsorbed Zn. These experiments were carried out using a high ionic strength Na background electrolyte that enables one to block cation exchange processes and to restrict the Zn uptake to the sorption complexation at the edge sites of clay. The analysis of the experimental data and simulation results suggest that structurally incorporated Zn preferentially substitutes for Al(III) in the trans-symmetric sites of the octahedral layer. At low loading, Zn is incorporated into the outermost trans-octahedra on (010) and (110) edges. At medium loading, Zn forms mono- and bidentate inner-sphere surface complexes attached to the octahedral layer of (010) and (110) edge sites. The maximal site density of inner-sphere sorption sites inferred from molecular simulations agrees well with site capacities of surface complexation sites derived from macroscopic studies and modeling.

Iodine species uptake by cement and CSH studied by I K-edge X-ray absorption spectroscopy

Summary The uptake of iodine species (I−/IO3−) by HCP (hardened cement paste) and a CSH (calcium silicate hydrate) phase under highly alkaline conditions has been investigated using X-ray absorption spectroscopy (XAS). The study was performed at the I K-edge (33.169 keV) instead of the I L3-edge (4.557 keV) to avoid interference with Ca (K-edge=4.038 keV), a major element in HCP and CSH phases. The XANES (X-rays absorption near-edge structure) spectra revealed no changes in the formal oxidation state of iodide (I(-I)−) and iodate (I(V)O3−) upon uptake by HCP and CSH. The EXAFS (extended X-ray absorption fine structure) oscillations from I− treated HCP and CSH samples were found to be extremely weak, limiting interpretation of the EXAFS data. The IO3− EXAFS spectra showed that the IO3− entity consisting of three oxygen atoms with a characteristic I-O distance (∼1.78 Å) is maintained upon uptake by HCP and CSH. XANES further indicated that CSH is not the uptake-controlling phase in HCP.

EXAFS study of Nd(III) uptake by amorphous calcium silicate hydrates (C-S-H)

Calcium silicate hydrate (C-S-H) phases control the immobilization of many metal cations in cementitious materials. In this study Nd binding to amorphous C-S-H phases with different Ca/Si (C/S) mol ratios (0.56, 0.87 and 1.54) and Nd loadings (7 and 35mumol/g), and which had been aged up to 270 days, has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The structural parameters derived from EXAFS were compared with those predicted from bond-valence calculations. The study reveals that Nd may form several species in contact with C-S-H phases. The EXAFS parameters determined in samples after one day of reaction indicate the formation of inner-sphere surface complexes. The Nd-Ca and Nd-Si bond-distances tend to increase with time at both Nd loadings. Changes in the coordination numbers N(Si) and N(Ca) were found to be dependent on the (C/S) ratio. At the lowest C/S ratio the number of neighboring Si atoms tends to increase with time while the number of neighboring Ca atoms tends to increase with time at highest C/S ratio. No clear trend was observed for the medium C/S ratio. Nd incorporation into the structures of C-S-H phases is assumed to be the dominant immobilization process based on comparison with bond-distances predicted from structural considerations. After prolonged reaction times (45 days) Nd is expected to be predominantly incorporated into the Ca sheets of the C-S-H structure while small portions of Nd might also be taken up by the interlayer. The study suggests that, in the long term, amorphous C-S-H phases are capable of taking up Nd via exchange processes with Ca(2+) in the Ca sheets and the interlayer.

Structural Insight into Iodide Uptake by AFm Phases

The ability of cement phases carrying positively charged surfaces to retard the mobility of (129)I, present as iodide (I(-)) in groundwater, was investigated in the context of safe disposal of radioactive waste. (125)I sorption experiments on ettringite, hydrotalcite, chloride-, carbonate- and sulfate-containing AFm phases indicated that calcium-monosulfate (AFm-SO(4)) is the only phase that takes up trace levels of iodide. The structures of AFm phases prepared by coprecipitating iodide with other anions were investigated in order to understand this preferential uptake mechanism. X-ray diffraction (XRD) investigations showed a segregation of monoiodide (AFm-I(2)) and Friedels salt (AFm-Cl(2)) for I-Cl mixtures, whereas interstratifications of AFm-I(2) and hemicarboaluminate (AFm-OH-(CO(3))(0.5)) were observed for the I-CO(3) systems. In contrast, XRD measurements indicated the formation of a solid solution between AFm-I(2) and AFm-SO(4) for the I-SO(4) mixtures. Extended X-ray absorption fine structure spectroscopy showed a modification of the coordination environment of iodine in I-CO(3) and in I-SO(4) samples compared to pure AFm-I(2). This is assumed to be due to the introduction of stacking faults in I-CO(3) samples on one hand and due to the presence of sulfate and associated space-filling water molecules as close neighbors in I-SO(4) samples on the other hand. The formation of a solid solution between AFm-I(2) and AFm-SO(4), with a short-range mixing of iodide and sulfate, implies that AFm-SO(4) bears the potential to retard (129)I.

Uptake of Np(IV) by C–S–H Phases and Cement Paste: An EXAFS Study

Nuclear waste disposal concepts developed worldwide foresee the use of cementitious materials for the immobilization of long-lived intermediate level waste (ILW). This waste form may contain significant amounts of neptunium-237, which is expected to be present as Np(IV) under the reducing conditions encountered after the closure of the repository. Predicting the release of Np(IV) from the cementitious near field of an ILW repository requires a sufficiently detailed understanding of its interaction with the main sorbing components of hardened cement paste (HCP). In this study, the uptake of Np(IV) by calcium silicate hydrates (C-S-H) and HCP has been investigated using extended X-ray absorption fine structure (EXAFS) spectroscopy. The EXAFS studies on Np(IV)-doped C-S-H and HCP samples reveal that Np(IV) is predominantly incorporated in the structure of C-S-H phases having different Ca:Si ratios. The two main species identified correspond to Np(IV) in C-S-H with a Ca:Si mol ratio of 1.65 as in fresh cement and with a Ca:Si mol ratio of 0.75 as in highly degraded cement. The local structure of Np(IV) changes with the Ca:Si mol ratio and does not depend on pH. Furthermore, Np(IV) shows the same coordination environment in C-S-H and HCP samples. This study shows that C-S-H phases are responsible for the Np(IV) uptake by cementitious materials and further that incorporation in the interlayer of the C-S-H structure is the dominant uptake mechanism.

Ni clay neoformation on montmorillonite surface.

Polarized extended X-ray absorption fine structure spectroscopy (P-EXAFS) was used to study the sorption mechanism of Ni on the aluminous hydrous silicate montmorillonite at high ionic strength (0.3 M NaClO4), pH 8 and a Ni concentration of 0.66 mM. Highly textured self-supporting clay films were obtained by slowly filtrating a clay suspension after a reaction time of 14 days. P-EXAFS results indicate that sorbed Ni has a Ni clay-like structural environment with the same crystallographic orientation as montmorillonite layers.

Ni phases formed in cement and cement systems under highly alkaline conditions: an XAFS study

X-ray absorption fine structure (XAFS) spectroscopy was applied to assess the solubility-limiting phase of Ni in cement and cement minerals. The study reveals the formation Ni and Al containing hydrotalcite-like layered double hydroxides (Ni-Al LDHs) when cement material (a complex mixture of CaO, SiO2, Al2O3, Fe2O3 and SO3) was treated with Ni in artificial cement pore water under highly alkaline conditions (pH = 13.3). This finding indicates that Ni-Al LDHs and not Ni-hydroxides determine the solubility of Ni in cement materials.

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).