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.     

Structural characterization of U(VI) surface complexes on kaolinite in the presence of humic acid using EXAFS spectroscopy

To determine the influence of humic acid (HA), pH, and presence of atmospheric CO2 on the sorption of U(VI) onto kaolinite, the structure of the surface complexes was studied by U L III-edge extended X-ray absorption fine structure (EXAFS) spectroscopy. The best fits to the experimental EXAFS data were obtained by including two uranium coordination shells with two axial (O ax) and five equatorial (O eq) oxygen atoms at 1.77+/-0.02 and 2.34+/-0.02 A, respectively, and two coordination shells with one Al/Si atom each at 3.1 and 3.3 A. As in the case of the binary system U(VI)-kaolinite, uranium forms inner-sphere surface complexes by edge sharing with aluminum octahedra and/or silicon tetrahedra. HA and atmospheric CO2 as well as pH had no influence on the EXAFS structural parameters in the pH range of 5-8. Despite the presence of HA, U(VI) prefers to sorb directly onto kaolinite and not to HA that is bound to the clay surface. X-ray photoelectron spectroscopy (XPS) measurements of kaolinite particles that had been exposed to HA suspensions showed that significant parts of the kaolinite surface are not covered by HA.     

Uranyl sorption onto gibbsite studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) was combined with batch experiments to study the sorption of uranium(VI) onto gibbsite (gamma-Al(OH)3). The experiments were performed under ambient conditions in 0.1 M NaClO4 solution in the pH range from 5.0 to 8.5 using a total uranium concentration of 1x10(-5) M, and a solid concentration of 0.5 g/40 ml. Two uranyl surface species with fluorescence lifetimes of 330+/-115 and 5600+/-1640 ns, respectively, were identified. The first species was dominating the more acid pH region whereas the second one became gradually more prominent towards higher pH values. The fluorescence spectra of both adsorbed uranyl(VI) surface species were described with six characteristic fluorescence emission bands situated at 479.5+/-1.1, 497.4+/-0.8, 518.7+/-1.0, 541.6+/-0.7, 563.9+/-1.2, and 585.8+/-2.1 nm. The surface species with the short-lived fluorescence lifetime of 330 ns is attributed to a bidentate mononuclear inner-sphere surface complex in which the uranyl(VI) is bound to two reactive OH- groups at the broken edge linked to one Al. The second surface species with the significant longer fluorescence lifetime of 5600 ns was attributed to small sorbed clusters of polynuclear uranyl(VI) surface species. The longer fluorescence lifetime of the long-lived uranyl surface species at pH 8.5 is explained with the growing average size of the adsorbed polynuclear uranyl surface species.     

Adsorption of barium(II) on montmorillonite: an EXAFS study

Migration of radioactive radium, ²²⁶Ra, in soil is an environmental concern, especially in areas adjacent to uranium processing facilities. Barium(II), as Ba²⁺, was used as a Ra analog and reacted with a Na-montmorillonite to obtain mechanistic insights into the interaction of Ra with soil matrices. The majority of sorbed Ba is associated with the permanently charged surface sites on the montmorillonite basal surface. This is indicated by the facts that (1) sorption of Ba(II) on montmorillonite is not highly sensitive to solution pH, although an increase of sorption was observed at higher pH values; and (2) displacement of sorbed Ba increased with increased NaNO₃ concentration. As demonstrated by EXAFS, a small fraction of Ba also adsorbed on the montmorillonite edge, forming an inner-sphere surface complex through sharing of oxygen atom(s) from deprotonated –OH group of the Al octahedral layer. The EXAFS measured distances between Ba and O at the first shell, and Ba and Al of the second shell are 2.7–2.8 and 3.7–3.9 Å, respectively, consistent with the results from geometry of a inner-sphere complex at the edge site. Results from bulk experiments and spectroscopic analysis suggest a co-existence of outer- and inner-sphere surface complexes for Ba sorbed to the montmorillonite surface.     

Simultaneous removal of uranium and humic acid by cyclodextrin modified graphene oxide nanosheets

Cyclodextrin-modified graphene oxide nanosheets (denoted as CD/GO) were synthesized by an in-situ polymerization method and characterized by as well as Fourier transform-infrared spectroscopy, X-ray photoelectron spectroscopy, Raman spectroscopy and potentiometric acid-base titration. The characterization results indicated that CD was successfully grafted onto GO surfaces by forming a chemical bond. Mutual effects on the simultaneous removal of hexavalent uranium and humic acid by CD/GO from aqueous solution were investigated. The results indicated that U(VI) and humic acid (HA) sorption on CD/GO were greatly affected by pH and ionic strength. The presence of HA enhanced U(VI) sorption at low pH and reduced U(VI) sorption at high pH, whereas the presence of U(VI) enhanced HA sorption. The surface adsorbed HA acted as a “bridge” between U(VI) and CD/GO, and formed strong inner-sphere surface complexes with U(VI). Sorption isotherms of U(VI) or HA on CD/GO could be well fitted by the Langmuir model. This work highlights that CD/GO can be used as a promising material in the enrichment of U(VI) and HA from wastewater in U(VI) and humic substances obtained by environmental pollution cleanup.     

Surface complexation modeling of uranium(VI) sorbed onto zirconium oxophosphate versus temperature: thermodynamic and structural approaches

This work presents an investigation of the interaction mechanisms between uranyl ions and a solid phosphate, the zirconium oxophosphate: Zr2O(PO4)2. Both thermodynamic and structural points of view are developed. Indeed, prior to any simulation of the retention data, it is necessary to precisely characterize the system under study in order to gain information at a molecular scale. First, the intrinsic surface properties of this synthetic compound have been investigated for different temperatures ranging from 25 to 90 degrees C. Mass and potentiometric titrations show that the surface site density remains constant between 25 and 90 degrees C, while the experimental point of zero charge slightly decreases from 4.8 to 4.5 with an increasing temperature. The potentiometric titration data are simulated, for each temperature, using the constant capacitance model and taking into account two surface sites ([TRIPLE BOND]ZrO and [TRIPLE BOND]PO) with a total surface site density equal to 7.0 sites nm(-2). For both reactive sites, the intrinsic protonation constants do not change with the temperature, while the deprotonation ones increase. These results led to the determination of the associated enthalpy and entropy changes according to the van't Hoff relation. Second, the speciation of U(VI) at the solid/solution interface has been studied using two complementary spectroscopic techniques probing the sorbed uranyl ions: time-resolved laser-induced fluorescence spectroscopy (TRLFS) and X-ray absorption spectroscopy (EXAFS). The substrate presents two different reactive surface sites against uranium retention, which are constituted by the oxygen atoms of the surface PO4 groups and the oxygen atoms linked to the zirconium atoms. Two inner-sphere complexes are thus present on the substrate, their relative proportion depending on the pH value of the suspension. The effects of the temperature (25-90 degrees C) on the surrounding uranium were checked using the TRLFS technique. The uranyl sorption constants onto the Zr2O(PO4)2 substrate were determined taking into account the structural investigation. The surface complexation modeling was performed using the constant capacitance model included in the FITEQLv4.0 code. The four adsorption edges obtained at 25, 50, 75, and 90 degrees C were simulated. The modeling of these experimental data was realized considering two surface complexes (([TRIPLE BOND]ZrOH)2UO(2+)2, ([TRIPLE BOND]PO)2UO2) according to the structural investigation. The constant value associated with the ZrO site does not change with the temperature, while the one corresponding to the PO site increases. Finally, the enthalpy and entropy changes associated with the uranyl sorption constants have been determined using the van't Hoff relation.     

Sorption speciation of nickel(II) onto Ca-montmorillonite: batch, EXAFS techniques and modeling

The sorption speciation of Ni(II) on Ca-montmorillonite was evaluated using a combination of batch experiments, extended X-ray absorption fine structure (EXAFS) spectroscopy and modeling. The pH and temperature at the aqueous-montmorillonite interface affects both the extent of Ni(II) sorption as well as the local atomic structure of the adsorbed Ni(II) ions. At 0.001 mol L(-1) Ca(NO(3))(2) and low pH, the study reveals that the majority of Ni(II) is adsorbed in the interlayers of Ca-montmorillonite coordinated by six water molecules in an octahedron as an outer-sphere complex. At higher pH, inner-sphere surface complexes are formed. The Ni-Si/Al distances (R(Ni-Al) = 3.00 ?, R(Ni-Si1) = 3.10 ? and R(Ni-Si2) = 3.26 ?) determined by EXAFS confirm the formation of mononuclear complexes located at the edges of Ca-montmorillonite platelets at pH 7.5 and 8.5. At pH 10.0, the Ni-Ni/Si distances (R(Ni-Ni) = 3.07 ? and R(Ni-Si) = 3.26 ?) indicates the formation of Ni-phyllosilicate precipitates. A rise in temperature promotes inner-sphere complexation, which in turn leads to an increase in Ni(II) sorption on Ca-montmorillonite. Sorption edges are fitted excellently by surface complexation model (SCM) with the aid of surface species determined from EXAFS spectroscopy.     

Interaction mechanisms between uranium(VI) and rutile titanium dioxide: from single crystal to powder

This paper is devoted to the study of the mechanisms of interaction between uranyl ion and rutile TiO2. Among the radionuclides of interest, U(VI) can be considered as a model of the radionuclides oxo-cations. The substrate under study here is the rutile titanium dioxide (TiO2) which is an interesting candidate as a methodological solid since it can be easily found as powder and as manufactured single crystals. This material presents also a wide domain of stability as a function of pH. Then, it allows the study of the retention processes on well-defined crystallographic planes, which can lead to a better understanding of the surface reaction mechanisms. Moreover, it is well-established that the (110) crystallographic orientation is dominating the surface chemistry of the rutile powder. Therefore, the spectroscopic results obtained for the U(VI)/rutile (110) system and other relevant crystallographic orientations were used to have some insight on the nature of the uranium surface complexes formed on rutile powder. This goal was achieved by using time-resolved laser-induced fluorescence spectroscopy (TRLFS) which allows the investigation, at a molecular scale, of the nature of the reactive surface sites as well as the surface species. For rutile surfaces, oxygen atoms can be 3-fold, 2-fold (bridging oxygens), or single-fold (top oxygens) coordinated to titanium atoms. However, among these three types of surface oxygen atoms, the 3-fold coordinated ones are not reactive toward water molecules or aqueous metallic cations. This study led to conclude on the presence of two uranium(VI) surface complexes: the first one corresponds to the sorption of aquo UO22+ ion sorbed on two bridging oxygen atoms, while the second one, which is favored at higher surface coverages, corresponds to the retention of UO22+ by one bridging and one top oxygen atom. Thus, the approach presented in this paper allows the establishment of experimental constraints that have to be taken into account in the modeling of the sorption mechanisms.     

Effects of sulfate ligand on uranyl carbonato surface species on ferrihydrite surfaces

Understanding uranium (U) sorption processes in permeable reactive barriers (PRB) are critical in modeling reactive transport for evaluating PRB performance at the Fry Canyon demonstration site in Utah, USA. To gain insight into the U sequestration mechanism in the amorphous ferric oxyhydroxide (AFO)-coated gravel PRB, U(VI) sorption processes on ferrihydrite surfaces were studied in 0.01 M Na(2)SO(4) solutions to simulate the major chemical composition of U-contaminated groundwater (i.e., [SO(4)(2-)] ~13 mM L(-1)) at the site. Uranyl sorption was greater at pH 7.5 than that at pH 4 in both air- and 2% pCO(2)-equilibrated systems. While there were negligible effects of sulfate ligands on the pH-dependent U(VI) sorption (<24 h) in both systems, X-ray absorption spectroscopy (XAS) analysis showed sulfate ligand associated U(VI) surface species at the ferrihydrite-water interface. In air-equilibrated systems, binary and mono-sulfate U(VI) ternary surface species co-existed at pH 5.43. At pH 6.55-7.83, a mixture of mono-sulfate and bis-carbonato U(VI) ternary surface species became more important. At 2% pCO(2), there was no contribution of sulfate ligands on the U(VI) ternary surface species. Instead, a mixture of bis-carbonato inner-sphere (38%) and tris-carbonato outer-sphere U(VI) ternary surface species (62%) was found at pH 7.62. The study suggests that the competitive ligand (bicarbonate and sulfate) coordination on U(VI) surface species might be important in evaluating the U solid-state speciation in the AFO PRB at the study site where pCO(2) fluctuates between 1 and 2 pCO(2)%.     

Interaction of uranium(VI) with phthalic acid

Phthalic acid, a ubiquitous organic compound found in soil, water, and in domestic and nuclear wastes can affect the mobility and bioavailability of metals and radionuclides. We examined the complexation of uranium with phthalic acid by potentiometric titration, electrospray ionization-mass spectroscopy (ESI-MS), and extended X-ray absorption fine structure (EXAFS) analysis. Potentiometric titration of a 1:1 U/phthalic acid indicated uranyl ion bonding with both carboxylate groups of phthalic acid; above pH 5 the uranyl ion underwent hydrolysis with one hydroxyl group coordinated to the inner-sphere of uranium. In the presence of excess phthalic acid, ESI-MS analysis revealed the formation of both 1:1 and 1:2 U/phthalic acid complexes. EXAFS studies confirmed the mononuclear biligand 1:2 U/phthalic acid complex as the predominant form. These results show that phthalates can form soluble stable complexes with uranium and may affect its mobility.     

Spectroscopic Evidence for Ternary Surface Complexes in the Lead(II)-Malonic Acid-Hematite System

Using extended X-ray absorption fine structure (EXAFS) and attenuated total reflectance Fourier-transform infrared (ATR-FTIR) measurements, we examined the sorption of Pb(II) to hematite in the presence of malonic acid. Pb L(III)-edge EXAFS measurements performed in the presence of malonate indicate the presence of both Fe and C neighbors, suggesting that a major fraction of surface-bound malonate is bonded to adsorbed Pb(II). In the absence of Pb(II), ATR-FTIR measurements of sorbed malonate suggest the formation of more than one malonate surface complex. The dissimilarity of the IR spectrum of malonate sorbed on hematite to those for aqueous malonate suggest at least one of the sorbed malonate species is directly coordinated to surface Fe atoms in an inner-sphere mode. In the presence of Pb, little change is seen in the IR spectrum for sorbed malonate, indicating that geometry of malonate as it coordinates to sorbed Pb(II) adions is similar to the geometry of malonate as it coordinates to Fe in the hematite surface. Fits of the raw EXAFS spectra collected from pH 4 to pH 8 result in average Pb-C distances of 2.98 to 3.14 ?, suggesting the presence of both four- and six-membered Pb-malonate rings. The IR results are consistent with this interpretation. Thus, our results suggest that malonate binds to sorbed Pb(II) adions, forming ternary metal-bridging surface complexes. Copyright 2001 Academic Press.     

Preconcentration of U(VI) ions on few-layered graphene oxide nanosheets from aqueous solutions

Graphene oxide nanosheets have attracted multidisciplinary attention due to their unique physicochemical properties. Herein, few-layered graphene oxide nanosheets were synthesized from graphite using a modified Hummers method and were characterized by TEM, AFM, Raman spectroscopy, XPS, FTIR spectroscopy, TG-DTA and acid-base titrations. The prepared few-layered graphene oxide nanosheets were used as adsorbents for the preconcentration of U(VI) ions from large volumes of aqueous solutions as a function of pH, ionic strength and temperature. The sorption of U(VI) ions on the graphene oxide nanosheets was strongly dependent on pH and independent of the ionic strength, indicating that the sorption was mainly dominated by inner-sphere surface complexation rather than by outer-sphere surface complexation or ion exchange. The abundant oxygen-containing functional groups on the surfaces of the graphene oxide nanosheets played an important role in U(VI) sorption. The sorption of U(VI) on graphene oxide nanosheets increased with an increase in temperature and the thermodynamic parameters calculated from the temperature-dependent sorption isotherms suggested that the sorption of U(vi) on graphene oxide nanosheets was an endothermic and spontaneous process. The maximum sorption capacities (Q(max)) of U(VI) at pH 5.0 ± 0.1 and T = 20 °C was 97.5 mg g(-1), which was much higher than any of the currently reported nanomaterials. The graphene oxide nanosheets may be suitable materials for the removal and preconcentration of U(VI) ions from large volumes of aqueous solutions, for example, U(VI) polluted wastewater, if they can be synthesized in a cost-effective manner on a large scale in the future.     

Sorption behaviour of uranium(VI) with N,N-dibutyl-N'-benzoylthiourea Impregnated in Amberlite XAD-16

The sorption of U(VI) by N, N-dibutyl, N'-benzoylthiourea (DBBT) impregnated resin has been studied. DBBT impregnated resin was prepared by direct adsorption of chelating ligand onto macroporous support, Amberlite XAD-16. The adsorption of DBBT on the macroporous support is shown by FTIR spectroscopy to be the result of only weak chelating ligand-support interactions. Parameters such as the pH effect on the sorption of uranium, the sorption capacity of the impregnated resin, the stripping of uranium and the effect of coexisting ions were investigated by batch experiments. The results demonstrated that uranium(VI) ions, at pH 4.5-7 could be sorbed completely using 0.1 g Amberlite XAD-16 resin loaded with DBBT. The sorption capacity of the impregnated resin is 0.90 mmol uranium(VI) g(-1). Quantitative recovery of U(VI) is achieved by stripping with 0.1 M HNO(3). The method was applied to the determination of uranium in synthetic samples. The precision of the method was 2.4 RSD% in a concentration of 1.20 mug ml(-1) for ten replicate analysis.     

Sorption speciation of lanthanides/actinides on minerals by TRLFS, EXAFS and DFT studies: a review

Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS), extended X-ray absorption fine structure spectroscopy (EXAFS) and density functional theory (DFT) is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III), Cm(III), U(VI), and Np(IV/VI) in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.     

Complexation of uranium(VI) with protocatechuic acid—application of iterative transformation factor analysis to EXAFS spectroscopy

The speciation of 1 mM uranium(VI) in carbonate-free aqueous solutions of 50 mM protocatechuic acid (PCA, 3,4-dihydroxybenzoic acid) was studied in the pH range of 4.0 to 6.8 using EXAFS spectroscopy. The uranium L_III-edge EXAFS spectra were analyzed using a newly developed computer algorithm for iterative transformation factor analysis (FA). Two structural different uranium(VI) complexes were observed. The speciation in the pH range of 4.0 to 4.8 is dominated by a 1:2 or 1:3 uranium(VI)/PCA complex with bidentate coordination of the carboxyl group to the uranium(VI) moiety. Already at pH 4.6 significant amounts of a second species are formed. This uranium(VI) species contains two PCA ligands that are bound to the uranium via their neighboring phenolic hydroxyl groups under formation of five-member rings.     

Influence of pH,soil humic acid,ionic strength and temperature on sorption of U(VI) onto attapulgite

The surface property of attapulgite was investigated by N₂-BET surface area and zeta potential analysis in this paper. Solution pH had a remarkable effect on the sorption process, indicated an inner-sphere complexation. Humic acid (HA) in the solution enhanced U(VI) sorption significantly at pH?<?5.0, while decreased U(VI) sorption obviously at pH?>?9.0. The characteristic fluorescence changes of HA indicated that a strong chemical reaction occurred between the functional groups in HA and UO₂²⁺. The sorption was a spontaneous and endothermic process with increased entropy, and the increase in temperature would benefit the sorption.     

Uranium(VI) Sorption Complexes on Montmorillonite as a Function of Solution Chemistry

We have investigated the effect of changes in solution chemistry on the nature of uranyl sorption complexes on montmorillonite (SAz-1) at different surface coverages (1.43-53.6 μmol/g). Uranyl uptake onto SAz-1 between pH 3 and 7 was determined in both titration and batch-mode experiments. These pH values result in solutions that contain a range of monomeric and oligomeric aqueous uranyl species. Continuous-wave and time-resolved emission spectroscopies were used to investigate the nature of U(VI) sorbed to SAz-1. A discrete set of uranyl surface complexes has been identified over a wide range of pH values at these low to moderate coverages. For all samples, two surface complexes are detected with spectral characteristics commensurate with an inner-sphere complex and an exchange-site complex; the relative abundance of these two species is similar over these pH values at low coverage (1.43-2.00 μmol/g). In addition, surface species having spectra consistent with polymeric hydroxide-like sorption complexes form at the moderate coverages ( approximately 34-54 μmol/g), increasing in abundance as the capacity of the amphoteric surface sites is exceeded. Furthermore, a species with spectral characteristics anticipated for an outer-sphere surface complex is observed for wet paste samples at low pH (3.7-4.4) and both low ( approximately 2 μmol/g) and moderate ( approximately 40 μmol/g) coverage. There are only subtle differences in the nature of sorption complexes formed at different pH values but similar coverages, despite markedly different uranyl speciation in solution. These results indicate that the speciation in the solution has minimal influence on the nature of the sorption complex under these experimental conditions. The primary control on the nature and abundance of the different uranyl sorption complexes appears to be the relative abundance and reactivity of the different sorption sites. Copyright 2001 Academic Press.     

Complex formation of uranium(VI) with the amino acids l-glycine and l-cysteine: A fluorescence emission and UV–Vis absorption study

The complexation of uranium(VI) with the amino acids l-glycine and l-cysteine has been investigated by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and UV–Vis spectroscopy at a low pH range. The identified 1:1 and 1:2 uranyl-l-glycine complexes fluoresce and have similar absorbance properties. In contrast to the glycine system, uranyl forms two different non-fluorescent 1:1 complexes with l-cysteine, showing individual absorbance properties under the given experimental conditions. The corresponding complex formation constants were calculated using the spectroscopic data.     

Removal of U(VI) from aqueous solutions by using MWCNTs and chitosan modified MWCNTs

In this paper, the multiwalled carbon nanotubes (MWCNTs) were modified with chitosan (CS) by using low temperature plasma grafting technique (denoted as MWCNT-CS). The prepared MWCNTs and MWCNT-CS were characterized by SEM, TEM, FTIR and Raman spectroscopy in detail and the results suggested that CS molecules were successfully grafted on the surfaces of MWCNTs. The materials were applied as adsorbents in the removal of U(VI) ions from large volumes of aqueous solutions as a function of environmental conditions. The removal of U(VI) from aqueous solution to MWCNTs and MWCNT-CS increased with increasing pH values at pH < 7, and then decreased with increasing pH values at pH > 7. The sorption of U(VI) on MWCNTs and MWCNT-CS was strongly dependent on pH and independent of ionic strength. The sorption of U(VI) on MWCNTs and MWCNT-CS was dominated by inner-sphere surface complexation rather than by ion exchange or outer-sphere surface complexation. The surface grafted chitosan molecules can enhances U(VI) sorption on MWCNTs obviously, which was also evidenced from the XPS spectroscopy analysis. The results of high sorption capacity of U(VI) on MWCNT-CS suggest that the MWCNT-CS nanomaterial is a suitable candidate in the preconcentration of U(VI) ions from large volumes of aqueous solutions.     

The complexation of uranium(VI) and atmospherically derived CO2 at the ferrihydrite-water interface probed by time-resolved vibrational spectroscopy

The sorption reactions of uranium(VI) at the ferrihydrite(Fh)-water interface were investigated in the absence and presence of atmospherically derived CO(2) by time-resolved in situ vibrational spectroscopy. The spectra clearly show that a single uranyl surface species, most probably a mononuclear bidentate surface complex, is formed irrespective of the presence of atmospherically derived CO(2). The character of the carbonate surface species correlates with the presence of the actinyl ions and changes from a monodentate to a bidentate binding upon sorption of U(VI). From the in situ sorption experiments under mildly acid conditions, the formation of a ternary surface complex is derived where the carbonate ligands coordinate bidentately to the uranyl moiety (≡UO(2)(O(2)CO)(x)). Furthermore, the release reaction of the carbonate ligands from the ternary surface complex is found to be considerably retarded compared to those from the pristine surface suggesting a tighter bonding of the carbonate ions in the ternary complex. Simultaneous sorption of U(VI) and atmospherically derived carbonate onto pristine Fh shows formation of binary monodentate carbonate surface complexes prior to the formation of the ternary complexes.