Characterization and quantification of Sm(III)/ and Cm(III)/clay mineral outer-sphere species by TRLFS in D2O and EXAFS studies

In order to assess the long-term safety of deep radioactive waste repositories, a precise characterization of the different sorption processes on a molecular basis and the exact definition of geochemical boundary conditions for their relevance are of immense importance. Through sorption on various minerals the migration of radionuclides will be hindered and their retention will be ensured. Using time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy, it was possible to identify outer-sphere sorbed trivalent lanthanides and actinides onto different montmorillonites and illite. Furthermore, the quantification of Cm(III)/clay outer-sphere sorption in D(2)O at different ionic strengths was shown. The results were confirmed by ion exchange model calculations. Finally, the structural parameters of a Sm(III)/clay outer-sphere complex were obtained by EXAFS measurements.     

An EXAFS and TRLFS investigation on uranium(VI) sorption to pristine and leached albite surfaces

Uranium(VI) was sorbed to freshly ground and leached albite in batch and flow-through systems in the pH range 5.0-6.4. The uranium(VI) surface complexes were studied by extended X-ray absorption fine structure (EXAFS) spectroscopy and time-resolved laser-induced fluorescence spectroscopy (TRLFS). The EXAFS analysis of uranium(VI) sorbed on albite at pH 5.8 and 5 x 10(-6) M U(VI) showed one silicon atom at a USi distance of 3.09 A, which is indicative of the formation of an inner-sphere, mononuclear, bidentate uranium(VI) surface complex, Si(O)2UO2, on the silicate tetrahedra of albite. Two additional uranium(VI) sorption complexes were detected by TRLFS at higher initial aqueous U(VI) concentrations. However, the structure of these surface complexes could not be derived from EXAFS, since the measured EXAFS spectra represent the average of two surface complex structures. In order to simulate U(VI) sorption onto weathered feldspar surfaces, albite was leached with 0.01 M HClO4, resulting in surface material similar to amorphous silica gel. EXAFS showed that the equatorial oxygen shell of uranium(VI) sorbed on this material at pH 5.0 and 5.8 was split in two distances of 2.23 and 2.44 A. This indicates the formation of an inner-sphere surface complex.     

Separation of actinides from Low Level Liquid Wastes (LLLW) by extraction chromatography using novel DMDOHEMA and TODGA impregnated resins

The uptake of several actinides [U(VI), Th(IV), Am(III), Cm(III)] and fission products was investigated from nitric acid solutions by two novel extraction chromatographic sorbents containing 2-(2-hexyloxy-ethyl)-N,N'-dimethyl-N,N'-dioctyl-malonamide (DMDOHEMA) and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA), respectively. The kinetics of the uptake of actinides was studied. The sorption of metal ions fromz simulated Low Level Liquid Waste (LLLW) solutions was evaluated. The results of these experiments revealed that the actinides and lanthanides could be separated from the bulk of other fission products in simulated LLLW solutions on both sorbents.This revised version was published online in November 2005 with corrections to the Cover Date.     

Time-resolved laser fluorescence spectroscopy and extended X-ray absorption spectroscopy investigations of the N3- complexation of Eu(III), Cm(III), and Am(III) in an ionic liquid: differences and similarities

The complexation of the lanthanide Eu(III) and the actinides Cm(III) and Am(III) by N3- was investigated by application of time-resolved laser fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (XAFS) in the ionic liquid solution of C4mimTf2N (1-butyl-3-methylimidazolium-bis(trifluoromethylsulfonyl)imide). TRLFS measurements show that the interaction of azide with Eu(CF3SO3)3 and Eu(ClO4)3 results in both dynamic luminescence quenching by collisional encounters of N3- with Eu(III) and static luminescence quenching by inner-sphere complexation of Eu(III) by N3-. Hereby, the complexation of Eu-triflate by azide starts at a lower N3- concentration as compared to the perchlorate salt. The authors ascribe this phenomenon to a stronger bonding of ClO4- toward the metal ion than triflate, as well as to a stronger electrostatic repulsion of N3- by the perchlorate ligand. In both actinide samples (Cm(ClO4)3, Am(ClO4)3), the complexation with azide exhibits a clear kinetic hindrance. Nevertheless, mixed actinide-perchlorate-azide complexes are formed after several days in C4mimTf2N. The different reaction kinetics for the Ln- and An-complexation by azide may provide the opportunity for an effective separation of lanthanides from actinides in the nuclear fuel cycle by the use of N-based extractants in ionic liquid solution.     

Differences of Eu(III) and Cm(III) chemistry in ionic liquids: investigations by TRLFS

In this study the coordination structure and chemistry of Eu(III) and Cm(III) in the ionic liquid C(4)mimTf(2)N (1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide) was investigated by time-resolved laser fluorescence spectroscopy (TRLFS). The dissolution of 1 x 10(-2) M Eu(CF(3)SO(3))(3) and 1 x 10(-7) M Cm(ClO(4))(3) in C(4)mimTf(2)N leads to the formation of two species for each cation with fluorescence emission lifetimes of 2.5 +/- 0.2 ms and 1.0 +/- 0.3 ms for the Eu-species and 1.0 +/- 0.3 ms and 300.0 +/- 50 micros for the Cm-species. The interpretation of the TRLFS data indicates a comparable coordination for both the lanthanide and actinide cation in this ionic liquid. The quenching influence of Cu(II) on the fluorescence emission of Eu(III) and Cm(III) was also measured by TRLFS. While Cu(ii) does not quench the Cm(III) fluorescence emission in C(4)mimTf(2)N the Eu(III) fluorescence emission lifetime for both Eu-species in C(4)mimTf(2)N decreases with increasing Cu(II) concentration. Stern-Volmer constants were calculated (k(SV) = 1.54 x 10(6) M(-1) s(-1) and k(SV) = 2.70 x 10(6) M(-1)). By contrast, the interaction of Cu(II) with Eu(III) and Cm(III) in water leads to a quenching of both the lanthanide and actinide fluorescence. The calculated Stern-Volmer constants are 1.20 x 10(4) M(-1) s(-1) for Eu(III) and 1.27 x 10(4) M(-1) s(-1) for Cm(III). The investigations show, while the chemistry of trivalent lanthanides and actinides is similar in an aqueous system it is dramatically different in ionic liquids. This difference in chemical behavior may provide the opportunity for a separation of lanthanides and actinides with regard to the reprocessing of nuclear fuel.     

Sorption of uranium (VI) species on zircon: structural investigation of the solid/solution interface

This work is an investigation of the mechanisms of interaction between uranium (VI) ions and zirconium silicate. The speciation of uranium (VI) sorbed on zircon was studied using four complementary techniques as probes of the local structure around the uranium atom: laser spectrofluorimetry, X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier-transformed (DRIFT) spectroscopy, and EXAFS spectroscopy. The sorption of uranyl on zirconium oxide was also studied to allow structural comparisons. Spectrofluorimetry and XPS results allowed an identification of the silicate sorption sites on the solid. These methods associated with spectrofluorimetry and DRIFT led to a characterization of the sorbed surface complexes, taking into account the influence of the nature of the background salt and of the pH on the structure of the U(VI) surface species. EXAFS measurements, either on air-dried samples or in situ, were then carried out on well-characterized samples and allowed identification of the sorption mechanism on zircon as the formation of an inner-sphere polydentate surface complex.     

Sorption Characteristics of Radioeuropium on Bentonite and Kaolinite

The factors affecting the sorption of radioeuropium(III) by bentonite and kaolinite were studied with the aim to assess the important factors which should be included in modeling of radioeuropium(III) migration in soils and sediments. Europium(III) is an analogue of trivalent actinides. The distribution coefficients of radioeuropium for sorption on bentonite and kaolinite from aqueous solutions were determined by using the batch method, and it was found that they were sensitive to the loading, the pH, the humic substance and the sorption direction. Thus, these sorption characteristics of radioeuropium on bentonite and kaolinite were found to be different from those of radiocobalt¹, and the mathematical modeling of trivalent lanthanides and actinides migration will be more complicated than that of radiocobalt. It is improbable that the migration modeling with a constant distribution coefficient will be successful in the case of trivalent lanthanides and actinides.     

Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using ¹³C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physio-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42 mmol g⁻¹ for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6 M HNO₃ medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t_1/2 values of <6 min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30 μg L⁻¹. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100 mL of distilled water (for actinides) followed by elution with 20 mL of 0.1 M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.     

High Sorption and Selective Extraction of Actinides from Aqueous Solutions

The selective elimination of long-lived radioactive actinides from complicated solutions is crucial for pollution management of the environment. Knowledge about the species, structures and interaction mechanism of actinides at solid–water interfaces is helpful to understand and to evaluate physicochemical behavior in the natural environment. In this review, we summarize recent works about the sorption and interaction mechanism of actinides (using U, Np, Pu, Cm and Am as representative actinides) on natural clay minerals and man-made nanomaterials. The species and microstructures of actinides on solid particles were investigated by advanced spectroscopy techniques and computational theoretical calculations. The reduction and solidification of actinides on solid particles is the most effective way to immobilize actinides in the natural environment. The contents of this review may be helpful in evaluating the migration of actinides in near-field nuclear waste repositories and the mobilization properties of radionuclides in the environment.     

Investigations of actinides in the context of final disposal of high-level radioactive waste: trivalent actinides in aqueous solution

The speciation of redox sensitive trivalent actinides Pu(III), Np(III), and U(III) has been studied in aqueous solution. The redox preparation, stabilization, and speciation of these trivalent actinides in aqueous systems are discussed here. The reductants investigated were rongalite, hydroxylamine hydrochloride, and acetohydroxamic acid and the An(III) species have been characterized by UV–Vis and XANES spectroscopy. The results show that the effectiveness of stabilization decreases generally in the order Pu(III) > Np(III) > U(III) and that the effectiveness of each reducing agent depends on the experimental conditions. More than 80 % of Pu(III) aquo species have been stabilized up to pH 5.5, whereas the Np(III) aquo ion could be stabilized in a pH range 0–2.5, and U(III) aquo ion is sufficiently stable at pH 1.0 and below over time periods suitable for experiments. However, this study gives a basis for the characterisation of the trivalent lighter actinides involved in complexation, sorption, and solid formation reactions in the future.     

Actinide behavior on crushed rock columns

The interactions of dissolved or colloidal actinides with tuffaceous rock are being studied at Los Alamos National Laboratory in support of the Nevada Nuclear Waste Storage Investigations project. We have used small columns of crushed tuff to obtain information on the sorption of neptunium, plutonium and americium during short (<1 day) time spans. Data from these experiments supplement information obtained from longer term batch-type experiments and provide insight concerning sorption kinetics, speciation, and colloid migration. We find that Np(V), Pu(VI) and Pu(V) show limited sorption on crushed tuff. Pu(IV) polymer and Am(III) are largely retained by the tuff, with a small fraction of the imput material moving through the column as colloids.     

Immobilization of trivalent actinides by sorption onto quartz and incorporation into siliceous bulk: investigations by TRLFS

The adsorption of Cm(III) on quartz is studied by time resolved laser fluorescence spectroscopy (TRLFS) in the pH range from 3.75 to 9.45. The raw spectra are deconvoluted into three single components. The first one has a peak maximum at 593.8 nm and can be attributed to the Cm(III) aquo ion with an emission lifetime of 68+/-3 micros. The second one corresponds to an adsorbed species and has a peak maximum at 601.4 nm and an emission lifetime of 123+/-10 micros. The peak maximum of the third component is shifted to higher wavelength (603.6 nm) while the lifetime remains constant. Additionally, the adsorption of Am(III) on quartz is investigated in batch experiments. Based on the spectroscopic data a sorption mechanism is suggested. In addition, the obtained Am uptake data and the Cm-TRLFS data are modeled simultaneously using a single site Basic Stern model in combination with the charge distribution concept of Pauling. The finally suggested model consists of two bidentate surface complexes where the second one is the product of hydrolysis of the first sorption species. In a separate set of experiments the influence of silicic acid at different concentrations on the Cm(III) speciation in a quartz system is investigated by TRLFS. In suspension silicic acid at low concentration (3.5x10(-4) mol/L) has no influence on the Cm(III) speciation. At high concentration (3.5x10(-2) mol/L) the Cm(III) speciation is definitely influenced. The results at higher concentration indicate the formation of Cm(III)/silicic acid complexes and the incorporation of Cm(III) into siliceous bulk. This is confirmed by measurements at a quartz single crystal surface. Moreover, these measurements indicate the formation of quartz/Cm(III)/silicic acid ternary complexes at the mineral surface.     

Interaction of radionuclides with natural and manmade materials using XAFS technique

The X-ray absorption fine structure (XAFS) technology has exhibited a very unique application in the study of sorption mechanism, chemical species and microstructures of radionuclides at the natural solid-water interfaces. In this review, the interaction mechanism of radionuclides with clay minerals and nanomaterials under different environmental conditions are summarized from the XAFS spectroscopy analysis. The coordination number and the bond distances of radionuclides, the oxidation-reduction reactions, the influence of humic substances and microorganisms on the species and structures of radionuclides at molecule level are reviewed and compared. This review is helpful to understand the interactions of radionuclides with oxides, natural clay minerals and nanomaterials, which is also crucial to evaluate the physicochemical behaviors of radionuclides in the natural environment.     

Cr(III) and Cr(VI) on-line preconcentration and determination with high performance flow flame emission spectrometry in natural samples

Methods for the on-line chromatographic preconcentration of Cr(III) and Cr(VI) have been developed. Cr(VI) has been preconcentrated on an RP C18 silica based column with tetrabutylammonium-bromide (TBABr) as ion-pairing agent. Specially for Cr(III) a new and effective preconcentration technique based on the sorption of Cr(III)-ions in a C18 column in presence of KH-phthalate has been developed. The efficiency of sample introduction into the atomic emission spectrometer could be improved by hydraulic high pressure nebulization. For the detection of chromium the acetylene/N(2)O flame has been used as a powerful emission spectrometric source. Applying these steps the detection limit (3sigma) could be improved to 25 pg/mL for Cr(III) and to 20 pg/mL for Cr(VI). The method has been applied for the chromium speciation in natural water samples.     

EXAFS study of mercury(II) sorption to Fe- and Al-(hydr)oxides. I. Effects of pH

The study of mercury sorption products in model systems using appropriate in situ molecular-scale probes can provide detailed information on the modes of sorption at mineral/water interfaces. Such studies are essential for assessing the influence of sorption processes on the transport of Hg in contaminated natural systems. Macroscopic uptake of Hg(II) on goethite (alpha-FeOOH), gamma-alumina (gamma-Al(2)O(3)), and bayerite (beta-Al(OH)(3)) as a function of pH has been combined with Hg L(III)-edge EXAFS spectroscopy, FTIR spectroscopy, and bond valence analysis of possible sorption products to provide this type of information. Macroscopic uptake measurements show that Hg(II) sorbs strongly to fine-grained powders of synthetic goethite (Hg sorption density Gamma=0.39-0.42 micromol/m(2)) and bayerite (Gamma=0.39-0.44 micromol/m(2)), while sorbing more weakly to gamma-alumina (Gamma=0.04-0.13 micromol/m(2)). EXAFS spectroscopy on the sorption samples shows that the dominant mode of Hg sorption on these phases is as monodentate and bidentate inner-sphere complexes. The mode of Hg(II) sorption to goethite was similar over the pH range 4.3-7.4, as were those of Hg(II) sorption to bayerite over the pH range 5.1-7.9. Conversion of the gamma-Al(2)O(3) sorbent to a bayerite-like phase in addition to the apparent reduction of Hg(II) to Hg(I), possibly by photoreduction during EXAFS data collection, resulted in enhanced Hg uptake from pH 5.2-7.8 and changes in the modes of sorption that correlate with the formation of the bayerite-like phase. Bond valence calculations are consistent with the sorption modes proposed from EXAFS analysis. EXAFS analysis of Hg(II) sorption products on a natural Fe oxyhydroxide precipitate and Al/Si-bearing flocculent material showed sorption products and modes of surface attachment similar to those for the model substrates, indicating that the model substrates are useful surrogates for the natural sediments.     

Sorption of Eu(III) on GMZ bentonite in the absence/presence of humic acid studied by batch and XAFS techniques

Bentonite has been extensively studied because of its strong sorption ability and low permeability. In this work, the Na-bentonite from Gaomiaozi County (China) has been characterized by XRD, FTIR and acid-base titration. The sorption of Eu(III) on Na-bentonite in the absence/presence of humic acid (HA) was studied at T = 25 ± 2 °C and in 0.01 mol/L NaClO₄ solution. The effects of pH, HA, contact time and initial Eu(III) concentrations were also investigated. The results indicate that the sorption of Eu(III) on Na-bentonite was dependent on pH values. The presence of HA had little effect on Eu(III) sorption at low pH values, but decreased Eu(III) sorption at high pH values. X-ray absorption fine structure spectroscopy (XAFS) was applied to characterize the local structural environment of the adsorbed Eu(III) on bare Na-bentonite and HA-bentonite hybrids. The results indicate that Eu(III) was bound to O atoms at a distance of about 2.39 Å at pH 4.15. The results are crucial for the evaluation of the sorption and migration of other trivalent lanthanides and actinides in bentonite as backfill materials.     

Molecular-level investigation into copper complexes on vermiculite: effect of reduction of structural iron on copper complexation

In this paper we present results that describe the speciation of Cu sorbed to the clay mineral vermiculite, with special attention to the effects of reduction on Cu sorption complexes. Sorption complexes were studied using powdered extended X-ray absorption fine structure (EXAFS) spectroscopy, polarized EXAFS spectroscopy, and X-ray diffraction (XRD). Ionic strength (I), background ion, and clay reduction (structural iron) were varied in the sorption samples. At low I EXAFS results indicate that Cu was surrounded by up to six water molecules sorbed in the interlayer of reduced vermiculite. EXAFS results from Cu-equilibrated reduced vermiculite with high I Ca background electrolyte revealed that Cu was surrounded by 4 O atoms at 1.95 Angatroms and 8 second shell O atoms at 3.14 Angstroms. Angular dependence of the second shell O atoms interpreted from the polarized-EXAFS spectra indicated that the atoms are out of plane from the basal plane of the vermiculite (inclined approximately 25 degrees from the ab plane). The local atomic environment and angular dependence of the EXAFS spectra suggest that the Cu atoms are adsorbed above the hexagonal cavities of the reduced clay mineral and form a Cu dimer in the interlayer. This adsorption mechanism was not observed in the non-reduced vermiculite under identical equilibration conditions. Our results provide molecular level evidence that Cu sorption mechanisms on vermiculite are dependent on solution conditions, such as redox potential and background electrolyte. These results can be used to develop better models of Cu sorption mechanisms on clay mineral surfaces.     

Reversed-phase partition chromatographic separation of minor actinides with bis(2-ethylhexyl) sulfoxide from acidic nitrate PUREX waste solutions

The uptake behavior of U(VI), Pu(IV), Am(III) and a few long-lived fission products from nitric acid media by bis(2-ethylhexyl) sulfoxide (BESO) adsorbed on Chromosorb has been studied U(VI), Pu(IV) and Zr(IV) are taken up appreciably as compared to trivalent actinides/lanthanides including some coexisting fission product contaminants which are weakly sorbed on the column. Chromosorb could be loaded with (1.12±0.03) g of BESO per g of the support. Maximum sorption is observed around 4–5 mol·dm^–3 HNO₃ for both U(VI) and Pu(IV), which are sorbed as their disolvates. The elution of (U(VI) and Pu(IV) from the metal loaded sorbent has also been optimized. Desorption of U(VI) is easily accomplished with dilute nitric acid (ca. 0.01 mol·dm^–3)while Pu(IV) is reductively stripped with 0.1 mol·dm^–3 NH₂OH·HCl. Effective sequential separation of U(VI), Pu(IV) and Am(III) from their several admixtures could be readily achieved from real medium and low level active acidic process raffinates.     

Uranium(VI) speciation by spectroscopy

The application of UV-Vis and time-resolved laser-induced fluorescence (TRLF) spectroscopies to direct speciation of uranium(VI) in environmental samples offers various prospects that have, however, serious limitations. While UV-Vis spectroscopy is probably not sensitive enough to detect uranium(VI) species in the majority of environmental samples, TRLFS is principially able to speciate uranium(VI) at very low concentration levels in the nanomol range. Speciation by TRLFS can be based on three parameters: excitation spectrum, emission spectrum and lifetime of the fluorescence emission process. Due to quenching effects, the lifetime may not be expected to be as characteristic as, e.g., the emission spectrum. Quenching of U(VI) fluorescence by reaction with organic substances, inorganic ions and formation of carbonate radicals is one important limiting factor in the application of U(VI) fluorescence spectroscopy. Fundamental photophysical criteria are illustrated using UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato species as examples.     

Macro- and micro-scale studies on U(VI) immobilization in hardened cement paste

Wet chemistry and synchrotron-based (micro-)spectroscopic investigations have been carried out to determine the uptake and speciation of U(VI) in hardened cement paste (HCP). The wet chemistry experiments included kinetic studies and the determination of the sorption isotherm. The latter measurements allowed conditions for linear sorption to be distinguished from those where precipitation occurred. Micro-X-ray fluorescence and X-ray absorption spectroscopy (μ-XRF/XAS) were used to determine the elemental distribution and the coordination environment of U(VI) in an intact HCP sample at the atomic level. The sample was prepared by in-diffusion of U(VI) into HCP over 9 months. Micro-XRF maps revealed a heterogeneous distribution of U(VI) in a ten micron thick layer on the surface of the HCP disk. Micro-XAS measurements on a U(VI) hot spot showed that the coordination environment of U(VI) is similar to that in U(VI) doped HCP and in C-S-H sorption samples. To the best of our knowledge this is the first synchrotron-based micro-spectroscopic study on the speciation of diffusing uranyl ions with micro-scale spatial resolution.