Electrolyte layering at the calcite(104)-water interface indicated by Rb(+)- and Se(VI) K-edge resonant interface diffraction.

Calcite-water interface reactions are of major importance in various environmental settings as well as in industrial applications. Here we present resonant interface diffraction results on the calcite(104)-aqueous solution interface, measured in solutions containing either 10 mmol L(-1) RbCl or 0.5 mmol L(-1) Se(VI). Results indicate that Rb(+) ions enter the surface adsorbed water layers and adsorb at the calcite(104)-water interface in an inner-sphere fashion. A detailed analysis based on specular and off-specular resonant interface diffraction data reveals three distinct Rb(+) adsorption species: one 1.2 Å above the surface, the second associated with surface adsorbed water molecules 3.2 Å above the surface, and the third adsorbed in an outer-sphere fashion 5.6 Å above the surface. A peak in resonant amplitude between L = 1.5 and L = 3.0 is interpreted as signal from a layered electrolyte structure. The presence of a layered electrolyte structure seems to be confirmed by data measured in the presence of Se(VI).

Impact of the degradation leachate of the polyacrylonitrile-based material UP2W on the retention of Ni(II), Eu(III) and Pu(IV) by cement.

The uptake of 63Ni(II), 152Eu(III) and 242Pu(IV) by hardened cement paste (HCP, CEM I) in the degradation stage II (pH ≈ 12.5, [Ca] ≈ 0.02 M) was investigated in the presence of a degradation leachate of UP2W, a polyacrylonitrile-based (PAN) material used as a filter aid in nuclear power plants. The degradation leachate with a concentration of dissolved organic carbon of ∼40 ppm was obtained from the degradation of UP2W in portlandite-buffered solutions for ca. 1100 days. Redox conditions in the Pu systems were buffered with hydroquinone, which defines mildly reducing conditions (pe + pH ≈ 10) where Pu(IV) is the predominant oxidation state. The degradation leachate investigated in this work is moderately sorbed by cement, with distribution ratios (Rd) of (0.35 ± 0.15) m3 kg-1. These values are 30 to 100 times greater than distribution ratios previously reported for proxy ligands of PAN degradation products, i.e., glutaric acid, α-hydroxyisobutyric acid and 3-hydroxybutyric acid. The presence of the degradation leachate induces a moderate decrease in the uptake of 63Ni(II), 152Eu(III) and 242Pu(IV) by cement, as compared to the sorption in the presence of the proxy ligands. Nevertheless, retention in the presence of the degradation leachate remains high for all investigated radionuclides, with Rd(63Ni(II)) ≈ 2 m3 kg-1, Rd(152Eu(III)) ≈ 100 m3 kg-1 and Rd(242Pu(IV)) ≈ 30 m3 kg-1. These observations possibly reflect that the multiple functionalities (-COOH, -OH, amide groups) expected in the macromolecules (10-15 kDa) present in the degradation leachate, can offer further binding/chelating capabilities compared to the small organic proxy ligands with at most bidentate binding.

Selenide retention by mackinawite.

The isotope (79)Se may be of great concern with regard to the safe disposal of nuclear wastes in deep geological repositories due to its long half-life and potential mobility in the geosphere. The Se mobility is controlled by the oxidation state: the oxidized species (Se(IV)) and (Se(VI)) are highly mobile, whereas the reduced species (Se(0) and Se(-II)) form low soluble solids. The mobility of this trace pollutant can be greatly reduced by interacting with the various barriers of the repository. Numerous studies report on the oxidized species retention by mineral phases, but only very scarce studies report on the selenide (Se(-II)) retention. In the present study, the selenide retention by coprecipitation with and by adsorption on mackinawite (FeS) was investigated. XRD and SEM analyses of the samples reveal no significant influence of Se on the mackinawite precipitate morphology and structure. Samples from coprecipitation and from adsorption are characterized at the molecular scale by a multi-edge X-ray absorption spectroscopy (XAS) investigation. In the coprecipitation experiment, all elements (S, Fe, and Se) are in a low ionic oxidation state and the EXAFS data strongly point to selenium located in a mackinawite-like sulfide environment. By contacting selenide ions with FeS in suspension, part of Se is located in an environment similar to that found in the coprecipitation experiment. The explanation is a dynamical dissolution-recrystallization mechanism of the highly reactive mackinawite. This is the first experimental study to report on selenide incorporation in iron monosulfide by a multi-edge XAS approach.

Solubility of Ca(II), Ni(II), Nd(III) and Pu(IV) in the presence of proxy ligands for the degradation of polyacrylonitrile in cementitious systems.

The solubility of Ca(OH)2(cr), ß-Ni(OH)2(cr), Nd(OH)3(s) and PuO2(ncr, hyd) was investigated in cement porewater solutions containing glutarate (GTA), α-hydroxyisobutarate (HIBA) and 3-hydroxybutarate (HBA). These ligands were proposed as probable degradation products of UP2W, a polyacrylonitrile-based filter aid used in nuclear power plants. Results obtained in this work are compared with reported solubility data in the presence of iso-saccharinic acid (ISA), a polyhydroxocarboxylic acid resulting from cellulose degradation. None of the investigated proxy ligands shows any significant impact on the solubility of Ca(II), Nd(III) or Pu(IV) in cement porewater solutions. Although the formation of binary complexes M-L (M = Ca(II), Nd(III), An(IV); L = GTA, HIBA, HBA) under acidic conditions is described in the literature, these organic ligands cannot outcompete hydrolysis under hyperalkaline conditions. GTA, HIBA and HBA induce a slight increase in the solubility of ß-Ni(OH)2(cr) at [L]tot = 0.1 M. This observation supports the formation of stable Ni(II)-GTA, -HIBA and -HBA complexes in hyperalkaline conditions, although the exact stoichiometry of these complexes remains unknown. The comparison of these results with solubility data in the presence of ISA confirms the stronger complexation properties of the latter ligand. Even though HIBA and HBA are carboxylic acids containing one alcohol group, this comparison shows that additional alcohol groups are required to efficiently chelate the metal ion and outcompete hydrolysis. This conclusion is supported by DFT calculations on the Pu(IV)-OH-L systems (L = GTA, HIBA and HBA), which indicate that the complexation with the proxy ligands takes places through the carboxylate group. XRD of selected solid phases after equilibration with proxy ligands at [L]tot = 0.1 M confirms that Ca(II), Ni(II), Nd(III) and Pu(IV) starting solid materials remained mostly unaltered in the course of the experiments. However, the presence of new XRD features suggests the possible formation of secondary phases. These results allow assessment of the effect of the proposed proxy ligands on the solubility of key radionuclides and metal ions in cementitious systems relevant for low and intermediate level waste, and feed into on-going sorption studies evaluating the impact of UP2W degradation products on the uptake of radionuclides by cement.

Humic acid metal cation interaction studied by spectromicroscopy techniques in combination with quantum chemical calculations.

Humic acids (HA) have a high binding capacity towards traces of toxic metal cations, thus affecting their transport in aquatic systems. Eu(III)-HA aggregates are studied by synchrotron-based scanning transmission X-ray microscopy (STXM) at the carbon K-edge and laser scanning luminescence microscopy (LSLM) at the (5)D(0) --> (7)F(1,2) fluorescence emission lines. Both methods provide the necessary spatial resolution in the sub-micrometre range to resolve characteristic aggregate morphologies: optically dense zones embedded in a matrix of less dense material in STXM images correspond to areas with increased Eu(III) luminescence yield in the LSLM micrographs. In the C 1s-NEXAFS of metal-loaded polyacrylic acid (PAA), used as a HA model compound, a distinct complexation effect is identified. This effect is similar to trends observed in the dense fraction of HA/metal cation aggregates. The strongest complexation effect is observed for the Zr(IV)-HA/PAA system. This effect is confirmed by quantum chemical calculations performed at the ab initio level for model complexes with different metal centres and complex geometries. Without the high spatial resolution of STXM and LSLM and without the combination of molecular modelling with experimental results, the different zones indicating a ;pseudo'-phase separation into strong complexing domains and weaker complexing domains of HA would never have been identified. This type of strategy can be used to study metal interaction with other organic material.

Interaction of Np(v) with borate in alkaline, dilute-to-concentrated, NaCl and MgCl2 solutions.

The interaction of Np(v) with borate was investigated in 0.1-5.0 M NaCl and 0.25-4.5 M MgCl2 solutions with 7.2 ≤ pHm ≤ 10.0 (pHm = -log[H+]) and 0.004 M ≤ [B]tot ≤ 0.16 M. Experiments were performed under an Ar-atmosphere at T = (22 ± 2) °C using a combination of under- and oversaturation solubility experiments, NIR spectroscopy, and extensive solid phase characterization. A bathochromic shift (≈5 nm) in the Np(v) band at λ = 980 nm indicates the formation of weak Np(v)-borate complexes under mildly alkaline pHm-conditions. The identification of an isosbestic point supports the formation of a single Np(v)-borate species in dilute MgCl2 systems, whereas a more complex aqueous speciation (eventually involving the formation of several Np(v)-borate species) is observed in concentrated MgCl2 solutions. The solubility of freshly prepared NpO2OH(am) remained largely unaltered in NaCl and MgCl2 solutions with [B]tot = 0.04 M within the timeframe of this study (t ≤ 300 days). At [B]tot = 0.16 M, a kinetically hindered but very significant drop in the solubility of Np(v) (3-4 log10-units, compared to borate-free systems) was observed in NaCl and dilute MgCl2 solutions with pHm ≤ 9. The drop in the solubility was accompanied by a clear change in the colour of the solid phase (from green to white-greyish). XRD and TEM analyses showed that the amorphous NpO2OH(am) "starting material" transformed into crystalline solid phases with similar XRD patterns in NaCl and MgCl2 systems. XPS, SEM-EDS and EXAFS further indicated that borate and Na/Mg participate stoichiometrically in the formation of such solid phases. Additional undersaturation solubility experiments using the newly formed Na-Np(v)-borate(cr) and Mg-Np(v)-borate(cr) compounds further confirmed the low solubility ([Np(v)]aq ≈ 10-6-10-7 M) of such solid phases in mildly alkaline pHm-conditions. The formation of these solid phases represents a previously unreported retention mechanism for the highly mobile Np(v) under boundary conditions (pHm, [B]tot, ionic strength) of relevance to certain repository concepts for nuclear waste disposal.

Application of asymmetric flow field-flow fractionation (AsFlFFF) coupled to inductively coupled plasma mass spectrometry (ICPMS) to the quantitative characterization of natural colloids and synthetic nanoparticles.

A straightforward quantification method is presented for the application of asymmetric flow field-flow fractionation (AsFlFFF) combined with inductively coupled plasma mass spectrometry (ICPMS) to the characterization of colloid-borne metal ions and nanoparticles. Reproducibility of the size calibration and recovery of elements are examined. Channel flow fluctuations are observed notably after initiation of the fractionation procedure. Their impact on quantification is considered by using (103)Rh as internal reference. Intensity ratios measured for various elements and Rh are calculated for each data point. These ratios turned out to be independent of the metal concentration and total sample solution flow introduced into the nebulizer within a range of 0.4-1.2 mL min(-1). The method is applied to study the interaction of Eu, U(VI) and Th with a mixture of humic acid and clay colloids and to the characterization of synthetic nanoparticles, namely CdSe/ZnS-MAA (mercaptoacetic acid) core/shell-coated quantum dots (QDs). Information is given not only on inorganic element composition but also on the effective hydrodynamic size under relevant conditions. Detection limits (DLs) are estimated for Ca, Al, Fe, the lanthanide Ce and the natural actinides Th and U in colloid-containing groundwater. For standard crossflow nebulizer, estimated values are 7 x 10(3), 20, 3 x 10(2), 0.1, 0.1 and 7 x 10(-2) microg L(-1), respectively. DLs for Zn and Cd in QD characterization are 28 and 11 microg L(-1), respectively.

Interaction of latex colloids with mineral surfaces and Grimsel granodiorite.

Bentonite clay is considered as possible backfill material for nuclear waste repositories in crystalline rock. The same material may also be a source of clay colloids, which may act as carriers for actinide ions possibly released from the repository. Depending on the geochemical parameters, these colloids may be retained by interaction with mineral surfaces of the host rock. In the present study interaction of carboxylated fluorescent latex colloids, used as a model for bentonite colloids, with natural Grimsel granodiorite and some of its component minerals is studied by fluorescence microscopy and SEM/EDX. The experiments are carried out by varying the pH from 2-10. Strong adsorption is observed at pH values close to or below the points of zero charge (pHpzc) of the mineral surfaces. The influence of Eu(III), used as a chemical homologue for trivalent actinide ions, on colloid adsorption is investigated. Depending on mineral phase and pH, a significant increase of colloid adsorption is observed in the presence of Eu(III).

The influence of colloid formation in a granite groundwater bentonite porewater mixing zone on radionuclide speciation.

In the context of deep geological storage of high level nuclear waste the repository will be designed as multiple barrier system including bentonite as buffer/backfill material and the host rock formation as geological barrier. The engineered barrier (bentonite) will be in contact with the host rock formation and consequently it can be expected that bentonite porewater will mix with formation groundwater. We simulate in this study the mixing of Grimsel groundwater (glacial melt water) with synthetic Febex porewater (assuming already saturated state) in a batch-type study and investigate the formation of colloids by laser-induced breakdown detection (LIBD) and SEM-EDX as well as the changes in radionuclide (U, Th, Eu) speciation via ultrafiltration or via time-resolved laser fluorescence spectroscopy (TRLFS) analysis in the case of Cm(III). Based on PHREEQC saturation index (SI) calculations a precipitation of calcite might be expected at low Febex porewater (FPW) content (<20%), fluorite precipitation at FPW contents <60% and gibbsite precipitation at FPW contents above 10%. The colloids generated in the mixing zone aggregate when the synthetic FPW content exceeds 10%. LIBD analysis of the time-dependent colloid generation/aggregation revealed a low concentration of colloids to be stable with an estimated plateau value around 100-200 ppt and an average colloid diameter around 30 nm after 140 days reaction time at FPW admixture >10%. SEM/EDX mostly identifies Al/Si containing colloidal phases and some sulfates could be found under certain admixture ratios. TRLFS studies show that the Cm speciation is strongly influenced by colloid formation in all solutions. In the Febex pore water/GGW mixing zone with high groundwater contents (>80%) colloids are newly formed and Cm is almost quantitatively associated with most likely polysilicilic acid colloids.

Thermodynamic description of Tc(iv) solubility and carbonate complexation in alkaline NaHCO3-Na2CO3-NaCl systems.

The solubility of 99Tc(iv) was investigated in dilute to concentrated carbonate solutions (0.01 M ≤ Ctot≤ 1.0 M, with Ctot = [HCO3-] + [CO32-]) under systematic variation of ionic strength (I = 0.3-5.0 M NaHCO3-Na2CO3-NaCl-NaOH) and pHm (-log[H+] = 8.5-14.5). Strongly reducing conditions (pe + pHm≈ 2) were set with Sn(ii). Carbonate enhances the solubility of Tc(iv) in alkaline conditions by up to 3.5 log10-units compared to carbonate-free systems. Solvent extraction and XANES confirmed that Tc was kept as +IV during the timeframe of the experiments (≤ 650 days). Solid phase characterization performed by XAFS, XRD, SEM-EDS, chemical analysis and TG-DTA confirmed that TcO2·0.6H2O(am) controls the solubility of Tc(iv) under the conditions investigated. Slope analysis of the solubility data in combination with solid/aqueous phase characterization and DFT calculations indicate the predominance of the species Tc(OH)3CO3- at pHm≤ 11 and Ctot≥ 0.01 M, for which thermodynamic and activity models are derived. Solubility data obtained above pHm≈ 11 indicates the formation of previously unreported Tc(iv)-carbonate species, possibly Tc(OH)4CO32-, although the likely formation of additional complexes prevents deriving a thermodynamic model valid for this pHm-region. This work provides the most comprehensive thermodynamic dataset available for the system Tc4+-Na+-Cl--OH--HCO3--CO32--H2O(l) valid under a range of conditions relevant for nuclear waste disposal.

Modeling the complexation properties of mineral-bound organic polyelectrolyte: an attempt at comprehension using the model system alumina/polyacrylic acid/M (M=Eu, Cm, Gd).

This paper contributes to the comprehension of kinetic and equilibrium phenomena governing metal ion sorption on organic-matter-coated mineral particles. Sorption and desorption experiments were carried out with Eu ion and polyacrylic acid (PAA)-coated alumina colloids at pH 5 in 0.1 M NaClO(4) as a function of the metal ion loading. Under these conditions, M interaction with the solid is governed by sorbed PAA (PAA(ads)). The results were compared with spectroscopic data obtained by time-resolved laser-induced fluorescence spectroscopy (TRLFS) with Cm and Gd. The interaction between M and PAA(ads) was characterized by a kinetically controlled process: after rapid metal adsorption within less than 1 min, the speciation of complexed M changed at the particle surface till an equilibrium was reached after about 4 days. At equilibrium, one part of complexed M was shown to be not exchangeable. This process was strongly dependent on the ligand-to-metal ratio. Two models were tested to explain the data. In model 1, the kinetically controlled process was described through successive kinetically controlled reactions that follow the rapid metal ion adsorption. In model 2, the organic layer was considered as a porous medium: the kinetic process was explained by the diffusion of M from the surface into the organic layer. Model 1 allowed a very good description of equilibrium and kinetic experimental data. Model 2 could describe the data at equilibrium but could not explain the kinetic data accurately. In spite of this disagreement, model 2 appeared more realistic considering the results of the TRLFS measurements.

The role of the 5f valence orbitals of early actinides in chemical bonding.

One of the long standing debates in actinide chemistry is the level of localization and participation of the actinide 5f valence orbitals in covalent bonds across the actinide series. Here we illuminate the role of the 5f valence orbitals of uranium, neptunium and plutonium in chemical bonding using advanced spectroscopies: actinide M4,5 HR-XANES and 3d4f RIXS. Results reveal that the 5f orbitals are active in the chemical bonding for uranium and neptunium, shown by significant variations in the level of their localization evidenced in the spectra. In contrast, the 5f orbitals of plutonium appear localized and surprisingly insensitive to different bonding environments. We envisage that this report of using relative energy differences between the 5fδ/φ and 5fπ*/5fσ* orbitals as a qualitative measure of overlap-driven actinyl bond covalency will spark activity, and extend to numerous applications of RIXS and HR-XANES to gain new insights into the electronic structures of the actinide elements.

CAT-ACT-A new highly versatile x-ray spectroscopy beamline for catalysis and radionuclide science at the KIT synchrotron light facility ANKA.

CAT-ACT-the hard X-ray beamline for CATalysis and ACTinide/radionuclide research at the KIT synchrotron radiation facility ANKA-is dedicated to X-ray spectroscopy, including "flux hungry" photon-in/photon-out and correlative techniques and combines state-of-the-art optics with a unique infrastructure for radionuclide and catalysis research. Measurements can be performed at photon energies varying between 3.4 keV and 55 keV, thus encompassing the actinide M- and L-edge or potassium K-edge up to the K-edges of the lanthanide series such as cerium. Well-established X-ray absorption fine structure spectroscopy in transmission and fluorescence detection modes is available in combination with high energy-resolution X-ray emission spectroscopy or X-ray diffraction techniques. The modular beamline design with two alternately operated in-line experimental stations enables sufficient flexibility to adapt sample environments and detection systems to many scientific challenges. The ACT experimental station focuses on various aspects of nuclear waste disposal within the mission of the Helmholtz association to contribute to the solution of one of the greatest scientific and social challenges of our time-the safe disposal of heat producing, highly radioactive waste forms from nuclear energy production. It augments present capabilities at the INE-Beamline by increasing the flux and extending the energy range into the hard X-ray regime. The CAT experimental station focuses on catalytic materials, e.g., for energy-related and exhaust gas catalysis. Characterization of catalytically active materials under realistic reaction conditions and the development of in situ and operando cells for sample environments close to industrial reactors are essential aspects at CAT.

Multielement characterization of metal-humic substances complexation by size exclusion chromatography, asymmetrical flow field-flow fractionation, ultrafiltration and inductively coupled plasma-mass spectrometry detection: a comparative approach.

The use of three different separation techniques, ultrafiltration (UF), high performance size exclusion chromatography (HPSEC) and asymmetrical flow field-flow fractionation (AsFlFFF), for the characterization of a compost leachate is described. The possible interaction of about 30 elements with different size fractions of humic substances (HS) has been investigated coupling these separation techniques with UV-vis absorption spectrophotometry and inductively coupled plasma-mass spectrometry (ICP-MS) as detection techniques. The organic matter is constituted by a polydisperse mixture of humic substances ranging from low molecular weights (around 1kDa) to significantly larger entities. Elements can be classified into three main groups with regard to their interaction with HS. The first group is constituted by primarily the monovalent alkaline metal ions and anionic species like B, W, Mo, As existing as oxyanions all being not significantly associated to HS. The second group consists of elements that are at least partly associated to a smaller HS size fraction (such as Ni, Cu, Cr and Co). A third group of mainly tri- and tetravalent metal ions like Al, Fe, the lanthanides, Sn and Th are rather associated to larger-sized HS fractions. The three separation techniques provide a fairly consistent size classification for most of the metal ions, even though slight disagreements were observed. The number-average molecular weight (Mn), the weight-average molecular weight (Mw) and the polydispersity (rho) parameters have been calculated both from AsFlFFF and HPSEC experiments and compared for HS and some metal-HS species. Differences in values can be partly explained by an overloading effect observed in the AsFlFFF experiments induced by electrostatic repulsion effects in the low ionic strength, high pH carrier solution. Size information obtained from ultrafiltration is not as resolved as for the other methods. Molecular weight cut-offs (MWCO) of the individual filter membranes refer to globular proteins and molecular weight information may therefore, deviate from that given by the other methods after calibration with polystyrene sulfonate (PSS) standards.

The INE-Beamline for actinide science at ANKA.

Since its inauguration in 2005, the INE-Beamline for actinide research at the synchrotron source ANKA (KIT North Campus) provides dedicated instrumentation for x-ray spectroscopic characterization of actinide samples and other radioactive materials. R&D work at the beamline focuses on various aspects of nuclear waste disposal within INE's mission to provide the scientific basis for assessing long-term safety of a final nuclear waste repository. The INE-Beamline is accessible for the actinide and radiochemistry community through the ANKA proposal system and the European Union Integrated Infrastructure Initiative ACTINET-I3. Experiments with activities up to 1 × 10(+6) times the European exemption limit are feasible within a safe but flexible containment concept. Measurements with monochromatic radiation are performed at photon energies varying between ~2.1 keV (P K-edge) and ~25 keV (Pd K-edge), including the lanthanide L-edges and the actinide M- and L3-edges up to Cf. The close proximity of the INE-Beamline to INE controlled area labs offers infrastructure unique in Europe for the spectroscopic and microscopic characterization of actinide samples. The modular beamline design enables sufficient flexibility to adapt sample environments and detection systems to many scientific questions. The well-established bulk techniques x-ray absorption fine structure (XAFS) spectroscopy in transmission and fluorescence mode have been augmented by advanced methods using a microfocused beam, including (confocal) XAFS/x-ray fluorescence detection and a combination of (micro-)XAFS and (micro-)x-ray diffraction. Additional instrumentation for high energy-resolution x-ray emission spectroscopy has been successfully developed and tested.

Characterization of acid-base properties of two gibbsite samples in the context of literature results.

Two different gibbsites, one commercial and one synthesized according to a frequently applied recipe, were studied in an interlaboratory attempt to gain insight into the origin of widely differing reports on gibbsite acid-base surface properties. In addition to a thorough characterization of the two solids, several methods relevant to the interfacial charging were applied to the two samples: potentiometric titrations to obtain the "apparent" proton related surface charge density, zeta-potential measurements characterizing the potential at the plane of shear, and Attenuated Total Reflection Infrared Spectroscopy (ATR-IR) to obtain information on the variation of counter-ion adsorption with pH (using nitrate as a probe). Values of the IEP at 9-10 and 11.2-11.3 were found for the commercial and synthesized sample, respectively. The experimental observations revealed huge differences in the charging behavior between the two samples. Such differences also appeared in the titration kinetics. A detailed literature review revealed similar disparity with no apparent systematic trend. While previously the waiting time between additions had been advocated to explain such differences among synthesized samples, our results do not support such a conclusion. Instead, we find that the amount of titrant added in each aliquot appears to have a significant influence on the titration curves. While we can relate a number of observations to others, a number of open questions and contradictions remain. We suggest various processes, which can explain the observed behavior.

Sorption of Eu(III) onto titanium dioxide: measurements and modeling.

In the present study, the sorption of europium and lutetium onto titanium dioxide from aqueous solutions is presented, as a function of pH, ionic strength and concentration. An acid base model for the titanium dioxide surface was determined from potentiometric titrations and zeta-potential measurements. The common intersection point of potentiometric titrations coincided with the isoelectric point from electrokinetic experiments, resulting in a pristine point of zero charge of about 6.1. The experimental data were in agreement with previously published results and a previously published MUSIC-type model was used as the basis to model the acid-base behavior. Comparison of europium and lutetium showed no difference in the adsorption behavior. Furthermore, no difference was observed both in uptake and spectroscopic studies whether carbonate was absent or present. The absence of a noticeable effect of the ionic strength on the adsorption behavior was indicative of strong binding. EXAFS revealed rough conservation of the coordination with 9-8 water and surface hydroxyl groups upon sorption. EXAFS results suggested the existence of different metal-oxygen distances, more varied than that observed for the respective aquo complex and thus indicative for inner-sphere surface complexation. A clear differentiation of surface complexation denticity was not possible based on spectroscopic data. A multisite surface complexation model approach was applied by assuming monodentate and multidentate binding to describe the trivalent metal uptake data. It is conceivable that mono- and multidentate species contribute to lanthanide sorption to titanium dioxide. In other words a distribution of states occurs in cation surface complexation reactions.

An attempt to explain bimodal behaviour of the sapphire c-plane electrolyte interface.

A tentative picture for the charging of the sapphire basal plane in dilute electrolyte solutions allows reconciliation of the available experimental observations within a dual charging model. It includes the MUltiSIte Complexation (MUSIC) model and auto-protolysis of interfacial water. The semi-empirical MUSIC model predicts protonation and deprotonation constants of individual surface functional groups based on crystal structure and bond-valence principles: on the ideal sapphire c-plane only doubly co-ordinated hydroxyl groups exist which cause quasi zero surface potential (defined as the potential in the plane of the surface hydroxyl groups) from pH 5 to 7 and rather weak charging beyond (compared to typical oxide behaviour). MUSIC predictions concur strikingly with recently published sum frequency data for the pH dependence of the so-called "ice-like" water band (interfacial water) and contact angle titrations. Zeta potential as well as second harmonic generation data reveal a sharp IEP of around 4 and a negative surface charge at the pristine point of zero charge predicted by the MUSIC model. New zeta-potential data corroborate (i) the low IEP and its insensitivity to salt concentration and (ii) the second harmonic results. We thus establish two groups of conflicting results arising from different techniques. A conventional model of the mineral electrolyte interface such as the MUSIC model is at odds with the negative zeta potentials in the pH range 5 to 7. Therefore an additional charging mechanism is invoked to explain all the observations. Enhanced auto-protolysis of interfacial water is the most probable candidate for this additional mechanism, in agreement with net water orientation observed with sum frequency generation and second harmonic generation. Our phenomenological explanation is further corroborated by the similarity of the zeta potential vs. pH curves of the c-plane with those of hydrophobic surfaces. Additional support comes from infrared spectroscopic data on thin water films on sapphire c-plane samples. Most stunningly, theoretical calculations on basal planes of this kind suggest a 2D water bilayer that makes such surfaces hydrophobic towards further adsorption of water. The proposed dual charging mode approach comprises the MUSIC model for protonation/deprotonation of the surface aluminols affecting the surface potential and the currently advocated enhanced auto-protolysis picture for hydrophobic surfaces controlling the zeta-potential and can explain the available information in a qualitative way. The respective contributions from the two components of this dual charging mechanism may be different for different single crystal cuts of alumina. Thus interplay between protonation/deprotonation of surface functional groups and auto-protolysis of interfacial water will cause the observed zeta potentials and isoelectric points. Repercussions of one mechanism on the other will result in the most favourable interfacial water structure, which can be followed by non-linear optic techniques like sum frequency generation.

Sorption of Cm(III) and Gd(III) onto gibbsite, alpha-Al(OH)(3): A batch and TRLFS study.

Gd(III) and Cm(III) sorption onto a pure aluminum hydroxide, gibbsite (alpha-Al(OH)(3)), is studied by batch experiments and time-resolved laser fluorescence spectroscopy (TRLFS). The experiments are conducted under argon atmosphere to exclude the influence of atmospheric CO(2) on solution and surface speciation. Batch experiments are done in two different electrolytes 0.1 M NaClO(4) and 0.1/0.01 M NaCl at a constant gibbsite concentration of 2.2 g/L. Gadolinium concentrations are varied from 6.4x10(-9) to 6.4x10(-5) M. pH-dependent sorption is found to be congruent at Gd(III) concentrations up to 6.4x10(-7) M and a shift of the pH edge to higher pH values is observed for higher metal ion concentrations. Type of background electrolyte anion and ionic strength do not affect the metal ion sorption. The spectroscopic investigations are performed with Cm(III) and gibbsite concentrations of 2x10(-7) M and 0.5 g/L, respectively. From the strongly red-shifted emission spectra two different inner-sphere surface complexes can be identified. A third species appearing at pH 6-11 is assigned to a coprecipitated or incorporated Cm(III) species. This incorporated species is most likely formed as a consequence of the applied experimental procedure. By continuously increasing the pH from 4 we move from high to low gibbsite solubility domains. As a result, aluminum hydroxide precipitates from oversaturated solutions, either covering already adsorbed curium or forming a Al/Cm(OH)(3) coprecipitate. Fluorescence lifetimes for the surface-bound Cm(III) complexes and the incorporated species are at 140-150 and 180-200 micros, respectively. Emission bands of the Cm(III) gibbsite surface complexes appear at comparable wavelengths as reported for Cm(III) species bound to aluminum oxides, e.g., gamma-Al(2)O(3); however, lifetimes are longer. This could presumably arise from either shorter binding distances of the Cm to Al-O sites or a coordination to more surface sites.

Sorption of Eu(III) on humic acid or fulvic acid bound to hydrous alumina studied by SEM-EDS, XPS, TRLFS, and batch techniques.

To identify the effect of humic acid (HA) and fulvic acid (FA) on the sorption mechanism of Eu(III) on organic--inorganic colloids in the environment at a molecular level, surface adsorbed/ complexed Eu(III) on hydrous alumina, HA-, and FA-hydrous alumina hybrids were characterized by using X-ray photoelectron spectroscopy (XPS) and time-resolved laser fluorescence spectroscopy (TRLFS). The experiments were performed in 0.1 mol/L KNO3 or 0.1 mol/L NaClO4 under ambient conditions. The pH values were varied between 2 and 11 at a fixed Eu(III) concentration of 6.0 x 10(-7) mol/L and 4.3 x 10(-5) mol/L. The different Eu(III)/FA(HA)/hydrous alumina complexes were characterized by their fluorescence emission spectra ((5D0-F1)/ (5D0 --> 7F2)) and binding energy of Eu(III). Inner-sphere surface complexation may contribute mainly to Eu(III) sorption on hydrous alumina, and a ternary surface complex is formed at the HA/ FA-hydrous alumina hybrid surfaces. The sorption and species of Eu(III) in ternary Eu-HA/FA-hydrous alumina systems are not dominated by either HA/FA or hydrous alumina, but are dominated by both HA/FA and hydrous alumina. The results are important for understanding the sorption mechanisms and the nature of surface adsorbed Eu(III) species and trivalent chemical homologues of Eu(III) in the natural environment.