Retention of Iodide by Chloride Green Rust and Magnetite.

Green rust (GR), a layered double hydroxide (LDH) containing Fe, and magnetite can be found in natural and engineered environments. The ability of chloride GR (GR-Cl) and magnetite to retain iodide as a function of various parameters was investigated. Sorption equilibrium is achieved within 1 day of contact time between iodide and preformed GR-Cl in suspension. pHm variations (7.5-8.5) have no significant influence, but the iodide sorption decreases with increasing ionic strength set by NaCl. Sorption isotherms of iodide suggest that the uptake operates via ionic exchange (IC), which is supported by geochemical modeling. The short-range binding environment of iodide associated with GR is comparable to that of hydrated aqueous iodide ions in solution and is not affected by pHm or ionic strength. This finding hints at an electrostatic interaction with the Fe octahedral sheet, consistent with weak binding of charge balancing anions within an LDH interlayer. The presence of sulfate anions in significant amounts inhibits the iodide uptake due to recrystallization to a different crystal structure. Finally, the transformation of iodide-bearing GR-Cl into magnetite and ferrous hydroxide resulted in a quantitative release of iodide into the aqueous phase, suggesting that neither transformation product has an affinity for this anionic species.

Combined X-ray absorption and SEM-EDX spectroscopic analysis for the speciation of thorium in soil.

Mobility and bioavailability of radionuclides in the environment strongly depend on their aqueous speciation, adsorption behavior and the solubility of relevant solid phases. In the present context, we focus on naturally occurring Th-232 at a location in central Sri Lanka presenting high background radiation levels. Four different soil samples were characterized using X-ray Absorption Spectroscopy (XAS) at the Th L3-edge (16.3 keV), Scanning Electron Microscopy (SEM) and Energy Dispersive X-ray (EDX) spectroscopy. X-ray Absorption Near Edge Structure (XANES) spectra are applied as a fingerprint indication for Th existing in different chemical environments. Linear combination fitting (LCF) of the Extended X-ray Absorption Fine Structure (EXAFS) data involving reference Th-monazite (phosphate) and thorianite (oxide) compounds suggested that Th is mostly present as Th-phosphate (76 ± 2%) and Th-oxide (24 ± 2%), even though minor amounts of thorite (silicate) were also detected by SEM-EDX. Further studies on selected individual particles using micro-focus X-ray Fluorescence (µ-XRF) and micro-X-ray Absorption Spectroscopy (µ-XAS) along with SEM-EDX elemental mapping provided information about the nature of Th-bearing mineral particles regarding mixed phases. This is the first study providing quantitative and XAS based speciation information on Th-mineral phases in soil samples from Sri Lanka.

Retention of Iodide and Chloride by Formation of a Green Rust Solid Solution GR-Cl1-xIx: A Multiscale Approach.

The uptake of iodide and chloride during the synthesis of green rust (GR), the Fe endmember of the layered double hydroxide (LDH) group, was investigated. GR compounds were prepared by aerial oxidation of Fe(OH)2 in suspension, considering various I/Cl ratios at constant ionic strength. Only GR compounds formed in all experiments, and the associated I/Cl ratio increased with that of the starting suspension. No preferential uptake of any halide could be detected, and all compounds had comparable morphology. Furthermore, the height of the interlayer gallery increased with the I/Cl ratio from ∼7.7 Šfor the chloride endmember to ∼8.3 Šfor the iodide endmember, and the observed linear increase was attributed to increasing interlayer iodide content. In all compounds, Fe K-edge X-ray absorption spectroscopy evidenced the presence of sixfold coordinated iron with a Fe2+/Fe3+ ratio of 3, homogeneously distributed within flattened octahedral sites, with six Fe as next-nearest neighbors. The Fe short-range environment was not affected by the interlayer composition, and no halide from the interlayer could be detected. Furthermore, iodide and chloride anions are located in a water-like environment, being loosely bound by weak electrostatic interactions to the octahedral sheet likely above ferric iron. Results consistently hint at the formation of a solid solution between chloride and iodide GR endmembers, certainly facilitated by the crystallization of both compounds in the same space group. This study provides further insights into the ability of LDH to simultaneously accommodate several anionic species of various sizes. The formation of such LDH compounds in a deep geological repository for nuclear waste thus represents a possible retention barrier to the migration to the far field of anionic species like 36Cl- and 129I- mobilized from the waste matrix. The extent of retention in disposal sites will depend, among others, on the availability of GR and on the concentration of competing anions.

Sorption of americium / europium onto magnetite under saline conditions: Batch experiments, surface complexation modelling and X-ray absorption spectroscopy study.

HYPOTHESIS: This study investigates the adsorption of americium and its chemical analogue europium on magnetite, which is expected to form as a major long-term steel canister corrosion product under anoxic and highly saline conditions. EXPERIMENTS: The sorption of europium on magnetite (solid/liquid ratio = 0.5 g/L) was investigated batch wise in NaCl brines with ionic strength I = 1 m, 3.5 m, and 6.67 m, as a function of pHm for two europium concentrations (6 × 10-10m, 1.2 × 10-5m). Information on the chemical nature of the surface species was obtained by X-ray absorption spectroscopy (XAS) at the americium L3-edge. FINDINGS: Retention of europium by magnetite of >99.5% was found above pHm 6.4 for all ionic strengths for europium concentration of 6 × 10-10m. No ionic strength effect was observed in this pHm range. At 1.2 × 10-5m europium concentration, 95 ± 4% sorption was found above pHm 7.5 for I = 1 m and above pHm 8.0 for I = 3.5 m and 6.67 m. A small ionic strength effect was observed in this case. X-ray absorption spectroscopy (XAS) results are consistent with the batch sorption experiment outcomes, showing an insignificant effect of ionic strength on the pHm dependent sorption. Results from potentiometric titrations of the solid phase, batch sorption experiments and spectroscopy were interpreted consistently with a charge distribution multi-site (CD-MUSIC) triple layer surface complexation model assuming surface coordination of the metal ion via a tridentate binding mode.

Adsorption of arsenic(V) onto single sheet iron oxide: X-ray absorption fine structure and surface complexation.

Adsorption onto two-dimensional nanosheet materials offers new possibilities for fast and efficient removal of contaminants from waters. Here, the adsorption of As(V) to a new type of iron oxides - single sheet iron oxide (SSI) - has been studied as a function of time, loading and pH. Adsorption of As(V) onto SSI was very fast compared to other iron oxides, with 80% of total As(V) adsorbed within 10 min. Examination by extended X-ray absorption fine structure analysis showed that As(V) forms a bidentate inner-sphere surface complex with SSI. Arsenic(V) adsorption isotherms and adsorption envelopes were well described using a 1-pK Basic Stern surface complexation model involving protonated (Fe2O2AsO2H-) and unprotonated (Fe2O2AsO2-2) inner-sphere surface complexes. The surface complexation constants for As(V) binding to SSI is similar to constants found for goethite and ferrihydrite. Simulated adsorption isotherms for intermediate As(V) concentrations also demonstrate that SSI is performing equally well as goethite and ferrihydrite based on surface area normalized adsorption capacities. The binding affinities at micromolar to submicromolar As(V) solution concentrations are similar for SSI and ferrihydrite. SSI has interesting potential as a stable, high-affinity sorbent for use in applications where efficient and fast removal is required.

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. II: insights from STEM-EDXS and DFT calculations.

Transformation products of two-line ferrihydrite associated with Lu(III) were studied after 12 years of aging using aberration-corrected high-angle annular dark field scanning transmission electron microscopy (HAADF-STEM), high-efficiency energy-dispersive X-ray spectroscopy (EDXS), and density functional theory (DFT). The transformation products consisted of hematite nanoparticles with overgrown goethite needles. High-efficiency STEM-EDXS revealed that Lu is only associated with goethite needles, and atomic-resolution HAADF-STEM reveals structural incorporation of Lu within goethite, partially replacing structural Fe sites. This finding corroborates those recently obtained by AsFlFFF and EXAFS spectroscopy on the same sample (Finck et al. 2018). DFT calculations indicate that Lu incorporation within goethite or hematite are almost equally likely, suggesting that experimental parameters such as temperature and reaction time which affect reaction kinetics, play important roles in determining the Lu uptake. It seems likely that these results may be transferable to predict the behavior of chemically homologous trivalent actinides.

Fate of Lu(III) sorbed on 2-line ferrihydrite at pH 5.7 and aged for 12 years at room temperature. I: insights from ICP-OES, XRD, ESEM, AsFlFFF/ICP-MS, and EXAFS spectroscopy.

Two-line ferrihydrite (2LFh) was aged for 12 years under ambient conditions and sheltered from light in the presence of Lu(III) used as surrogate for trivalent actinides. 2LFh aging produced hematite rhombohedra with overgrown acicular goethite particles. Analysis of the homogeneous suspension by asymmetrical flow field-flow fractionation (AsFlFFF) coupled to ICP-MS indicated that particles have a mean hydrodynamic diameter of about 140 nm and the strong correlation of the Fe and Lu fractograms hinted at a structural association of the lanthanide with the solid phase(s). Unfortunately, recoveries were low and thus results cannot be considered representative of the whole sample. The suspension was centrifuged and X-ray absorption spectroscopy (XAS) at the Lu L3-edge on the settled particles indicated that Lu(III) is sixfold coordinated by oxygen atoms, pointing to a retention by structural incorporation within particles. This result is consistent with AsFlFFF results on the same suspension without centrifugation. The detection of next nearest Fe and O atoms were consistent with the structure of goethite, ruling out incorporation within hematite. After centrifugation of the suspension, only nanoparticulate needle-like particles, very likely goethite, could be detected in the supernatant by ESEM. AsFlFFF data of the supernatant were comparable to that obtained for the homogeneous suspension, whereas XAS indicated that Lu(III) is predominantly present as dissolved species in the supernatant. Results from both techniques can be interpreted as a major fraction of Lu present as aqueous ions and a minor fraction as structurally incorporated. Findings from this study are corroborated by STEM-HAADF data and results from DFT calculations in a companion paper.

Adsorption of Selenium and Strontium on Goethite: EXAFS Study and Surface Complexation Modeling of the Ternary Systems.

Knowledge of the geochemical behavior of selenium and strontium is critical for the safe disposal of radioactive wastes. Goethite, as one of the most thermodynamically stable and commonly occurring natural iron oxy-hydroxides, promisingly retains these elements. This work comprehensively studies the adsorption of Se(IV) and Sr(II) on goethite. Starting from electrokinetic measurements, the binary and ternary adsorption systems are investigated and systematically compared via batch experiments, EXAFS analysis, and CD-MUSIC modeling. Se(IV) forms bidentate inner-sphere surface complexes, while Sr(II) is assumed to form outer-sphere complexes at low and intermediate pH and inner-sphere complexes at high pH. Instead of a direct interaction between Se(IV) and Sr(II), our results indicate an electrostatically driven mutual enhancement of adsorption. Adsorption of Sr(II) is promoted by an average factor of 5 within the typical groundwater pH range from 6 to 8 for the concentration range studied here. However, the interaction between Se(IV) and Sr(II) at the surface is two-sided, Se(IV) promotes Sr(II) outer-sphere adsorption, but competes for inner-sphere adsorption sites at high pH. The complexity of surfaces is highlighted by the inability of adsorption models to predict isoelectric points without additional constraints.

Uranium Redox Transformations after U(VI) Coprecipitation with Magnetite Nanoparticles.

Uranium redox states and speciation in magnetite nanoparticles coprecipitated with U(VI) for uranium loadings varying from 1000 to 10 000 ppm are investigated by X-ray absorption spectroscopy (XAS). It is demonstrated that the U M4 high energy resolution X-ray absorption near edge structure (HR-XANES) method is capable to clearly characterize U(IV), U(V), and U(VI) existing simultaneously in the same sample. The contributions of the three different uranium redox states are quantified with the iterative transformation factor analysis (ITFA) method. U L3 XAS and transmission electron microscopy (TEM) reveal that initially sorbed U(VI) species recrystallize to nonstoichiometric UO2+x nanoparticles within 147 days when stored under anoxic conditions. These U(IV) species oxidize again when exposed to air. U M4 HR-XANES data demonstrate strong contribution of U(V) at day 10 and that U(V) remains stable over 142 days under ambient conditions as shown for magnetite nanoparticles containing 1000 ppm U. U L3 XAS indicates that this U(V) species is protected from oxidation likely incorporated into octahedral magnetite sites. XAS results are supported by density functional theory (DFT) calculations. Further characterization of the samples include powder X-ray diffraction (pXRD), scanning electron microscopy (SEM) and Fe 2p X-ray photoelectron spectroscopy (XPS).

Morphology Controls on Calcite Recrystallization.

Environmental scientists and geoscientists working in different fields regard the reactivity of calcite and corresponding changes in its trace elemental- or isotopic composition from diametrically opposed points of view. As one extreme, calcite based environmental remediation strategies rely on the fast recrystallization of calcite and the concurrent uptake and immobilization of pollutants. Paleo-ecological investigations denote the other extreme, and rely on the invariability of calcite composition over geological periods of time. We use long-term radiotracer experiments to quantify recrystallization rates of seven types of calcite powder with diverse morphology and particle size distribution. On the one hand our results demonstrate the long-term metastability of calcite with equilibrated crystal surfaces even at isotopic dis-equilibrium. On the other hand, we document the extremely high reactivity and interfacial free energy of freshly ground, rough calcite. Our results indicate that bulk calcite recrystallization is an interfacial free energy driven Ostwald-ripening process, in which particle roughness effects dominate over the effect of crystal habitus and particle size. We confirm that the dynamic equilibrium exchange of crystal constituents between kink sites involves an activation barrier of about 25 kJ/mol. At room temperature the equilibrium exchange is limited to a near surface region and proceeds at a rate of (3.6 ± 1.4)·10-13 mol/(m2·s).

Trivalent Actinide Uptake by Iron (Hydr)oxides.

The retention of Am(III) by coprecipitation with or adsorption onto preformed magnetite was investigated by X-ray diffraction (XRD), solution chemistry, and X-ray absorption spectroscopy (XAS). In the coprecipitation experiment, XAS data indicated the presence of seven O atoms at 2.44(1) Å, and can be explained by an Am incorporation at Fe structural sites at the magnetite surface. Next-nearest Fe were detected at distances suggesting that Am and Fe polyhedra share corners in geometries ranging from bent to close to linear Am-O-Fe bonds. After aging for two years, the coordination number and the distance to the first O shell significantly decreased, and atomic shells were detected at higher distances. These data suggest a structural reorganization and an increase in structural order around sorbed Am. Upon contact with preformed Fe3O4, Am(III) forms surface complexes with cosorbed Fe at the surface of magnetite, a possible consequence of the high concentration of dissolved Fe. In a separate experiment, chloride green rust (GR) was synthesized in the presence of Am(III), and subsequently converted to Fe(OH)2(s) intermixed with magnetite. XAS data indicated that the actinide is successively located first at octahedral brucite-like sites in the GR precursor, then in Fe(OH)2(s), an environment markedly distinct from that of Am(III) in Fe3O4. The findings indicate that the magnetite formation pathway dictates the magnitude of Am(III) incorporation within this solid.

Interaction of selenite with reduced Fe and/or S species: An XRD and XAS study.

In this study, we investigated the interaction between selenite and either Fe((II))aq or S((-II))aq in solution, and the results were used to investigate the interaction between Se((IV))aq and FeS in suspension. The reaction products were characterized by a combination of methods (SEM, XRD and XAS) and the reaction mechanisms were identified. In a first experiment, Se((IV))aq was reduced to Se((0)) by interaction with Fe((II))aq which was oxidized to Fe((III)), but the reaction was only partial. Subsequently, some Fe((III)) produced akaganeite (ß-FeOOH) and the release of proton during that reaction decreased the pH. The pH decrease changed the Se speciation in solution which hindered further Se((IV)) reduction by Fe((II))aq. In a second experiment, Se((IV))aq was quantitatively reduced to Se((0)) by S((-II))aq and the reaction was fast. Two sulfide species were needed to reduce one Se((IV)), and the observed pH increase was due to a proton consumption. For both experiments, experimental results are consistent with expectations based on the oxidation reduction potential of the various species. Upon interaction with FeS, Se((IV))aq was reduced to Se((0)) and minute amounts of pyrite were detected, a consequence of partial mackinawite oxidation at surface sulfur sites. These results are of prime importance with respect to safe deep disposal of nuclear waste which contains the long-lived radionuclide (79)Se. This study shows that after release of (79)Se((IV)) upon nuclear waste matrix corrosion, selenite can be reduced in the near field to low soluble Se((0)) by interaction with Fe((II))aq and/or S((-II))aq species. Because the solubility of Se((0)) species is significantly lower than that of Se((IV)), selenium will become much less (bio)available and its migration out of deep HLW repositories may be drastically hindered.

Macroscopic and spectroscopic investigations on Eu(III) and Cm(III) sorption onto bayerite (ß-Al(OH)3) and corundum (α-Al2O3).

The interaction of trivalent Cm and Eu with the aluminum hydroxide bayerite (ß-Al(OH)3) and the aluminum oxide corundum (α-Al2O3) was investigated by batch sorption experiments and time resolved laser fluorescence spectroscopy (TRLFS). The experimental methods for both polymorphs show similar pH dependent sorption behavior at trace metal ion concentrations (∼10(-7) M), i.e. similar Eu sorption edges and nearly identical Cm speciation between pH=3 and 13. In this pH range the Cm aquo ion as well as the Cm(III) surface species surface⋯Cm(OH)x(H2O)(5-x) (x=0, 1, 2) can be distinguished by TRLFS. The similar sorption data point to a (surface) transformation of the thermodynamically unstable Al2O3 surface into bayerite, in agreement with the similar isoelectric points obtained for both minerals (pH(IEP)=8.6-8.8). The pH dependent surface charge is most likely due to the protonation/deprotonation of singly coordinated Al-OH surface groups, prevailing on the edge planes of the rod-like bayerite crystals and the surface of the colloidal Al2O3 particles. These surface groups are also believed to act as ligands for lanthanide/actinide(III) surface complexation. In contrast to the similar sorption behavior at trace metal ion concentrations, discrepancies are observed at higher Eu levels. While similar sorption edges occur up to 7×10(-7) M Eu for corundum, the pH edge on bayerite is gradually shifted to higher pH values in this Eu concentration range. The latter behavior may be related either to the existence of multiple sorption sites with different sorption affinities, or to the influence of an additional amorphous Al-phase, forming in the course of the bayerite synthesis.

Sites of Lu(III) sorbed to and coprecipitated with hectorite.

The Lu(III) binding mechanisms by trioctahedral smectite hectorite in aqueous systems were investigated by extended X-ray absorption fine structure (EXAFS) spectroscopy. Coprecipitated hectorite (Lu755Hec), its precursor phase (Lu/Brucite), and the surface sorbed hectorite (Lu/SHCa1) were prepared as oriented samples to collect polarized EXAFS (P-EXAFS) data. EXAFS analysis indicated that Lu(III) is 6-fold coordinated by oxygen in Lu/Brucite and in Lu755Hec, and surrounded by Mg/Si shells. The angular dependence of the O and Mg coordination numbers for Lu/Brucite hinted an Lu(III) incorporation in brucite layers. Mg and Si cationic shells were detected at distances suggesting a clay-like octahedral environment in Lu755Hec. EXAFS data for Lu/SHCa1 were consistent with Lu(III) forming inner-sphere surface complexes at hectorite platelets edges, but slightly above/below the octahedral plane. Finally, Lu(III) polyhedra share edge(s) and corner(s) with Si tetrahedra upon sorption to silica (Lu/Silica). Lu(III) binding to silicate oligomers or to silicate groups of the clay basal planes and formation of Lu(III) surface complexes during the coprecipitation experiment are marginal.

TRLFS characterization of Eu(III)-doped synthetic organo-hectorite.

Europium(III) was coprecipitated with the clay mineral hectorite, a magnesian smectite, following a multi-step synthesis procedure. Different Eu(III) species associated with the proceeding synthetic hectorite were characterized by selectively exciting the 5D0-->7F0 transition at low temperature (T < 20 K). Fluorescence decay times indicated that Eu(III) ions may be incorporated in the octahedral layer of the brucite precursor as well as in the octahedral sheet of the clay mineral. The excitation spectra indicated that the substitution of the divalent Mg by the trivalent Eu induced local structural deformation. This investigation implements the molecular-level understanding of the f element structural incorporation into the octahedral layer of sheet silicates by coprecipitation with clay minerals from salt solutions at 100 degrees C.