Time-resolved Laser Fluorescence Spectroscopy Study Research Articles

Uptake of Cm (III) and Eu (III) by C–S–H phases under saline conditions in presence of EDTA: A batch sorption and TRLFS study

Eu (III) and Cm (III) uptake by calcium silicate hydrate phases (C–S–H) was investigated in presence of EDTA in NaCl and CaCl2 solutions. Different experimental parameters, i.e., ionic strength (0.1 m ≤ I'm ≤ 5.05 m), ligand concentration (10−5 m ≤ [EDTA] ≤ 10−2 m), calcium-to-silicon ratio (0.6 ≤ C/S ≤ 1.3) and sorption time (7 d ≤ t ≤ 365 d) were varied in the frame of batch sorption experiments and Time Resolved Laser Fluorescence spectroscopy (TRLFS) measurements. No effect of EDTA on the retention of Eu(III)/Cm(III) by C–S–H phases in NaCl or CaCl2 systems was observed at ligand concentrations ≤ 10−3 M. In NaCl solutions with [EDTA] = 10−2 M and C/S < 1.3, low retention (log Rd = 2–3, with Rd in L∙kg−1) of Eu(III) was detected after 7 d of sorption time, while strong retention (log Rd = 5–6) was observed after 50 d. This behaviour was explained by the initial stabilization of Eu(III)/Cm(III) in the aqueous phase due to the formation of two aqueous Eu(III)/Cm(III)-(OH)n-EDTA complexes, followed by the slow incorporation of Eu(III)/Cm(III) into the C–S–H structure. In CaCl2 solutions for all C/S ratios, as well as in NaCl solutions for C/S ∼ 1.3, the presence of [EDTA] = 10−2 M led to a significant decrease of the uptake (log Rd = 2–3) after 7 and 50 d of contact time. This effect was explained by the formation of stable aqueous Ca–Eu(III)/Cm(III)-EDTA complexes triggered by the presence of moderate to high Ca concentrations. No evident effect caused by increased ionic strength conditions could be confirmed in our sorption experiments.Results obtained in batch sorption experiments are underpinned by TRLFS data, with the observation of three main aqueous species, tentatively defined as Cm(OH)(EDTA)2-, Cm(OH)x (EDTA)-(x+1) and Ca–Cm(III)-EDTA, as well as a fourth species corresponding to Cm(III) incorporated in the CaO-layer of the C–S–H phases. In spite of the thermodynamic stability of the CaEDTA2− complex, which reduces the concentration of free EDTA, the formation of ternary Ca–Eu(III)/Cm(III)-EDTA complexes is expected to result in a significant impact of EDTA on the uptake of An (III)/Ln (III) by cement at high ligand concentrations. The assumption that Ca outcompetes actinides for the complexation with EDTA in cementitious systems may need to be revisited under these conditions.

2,6-Bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine: Effects of the Peripheral Aliphatic Side Chain on the Coordination of Actinides(III) and Lanthanides(III).

To improve our understanding of the interaction mechanism in trivalent lanthanide and actinide complexes, studies with structurally different hard and soft donor ligands are of great interest. For that reason, the coordination chemistry of An(III) and Ln(III) with 2,6-bis(5-(tert-butyl)-1H-pyrazol-3-yl)pyridine (C4-BPP) has been explored. Time-resolved laser fluorescence spectroscopy (TRLFS) studies have revealed the formation of [Cm(C4-BPP)n]3+ (n = 1-3) (log β1' = 7.2 ± 0.4, log β2' = 10.1 ± 0.5, and log β3' = 11.8 ± 0.6) and [Eu(C4-BPP)m]3+ (m = 1-2) (log β1' = 4.9 ± 0.2 and log β2' = 8.0 ± 0.4). The absence of the [Eu(C4-BPP)3]3+ complex shows a more favorable complexation of Cm(III) over that of Eu(III). Additionally, complementary NMR measurements have been conducted to examine the M(III)-N bond in Ln(III) and Am(III) C4-BPP complexes. 15N NMR data have revealed notable differences in the chemical shifts of the coordinating nitrogen atoms between the Am(III) and Ln(III) complexes. In the Am(III) complex, the coordinating nitrogen atoms have shown a shift by 260 ppm, indicating a higher fraction of covalent bonding in the Am(III)-N bond compared with the Ln(III)-N bond. This observation aligns excellently with the differences in the stability constants obtained from TRLFS studies.

Uranium (VI) sorption on illite under varying carbonate concentrations: Batch experiments, modeling, and cryogenic time-resolved laser fluorescence spectroscopy study

Dissolved inorganic carbon (DIC) present in groundwaters can affect both the aqueous and surface species of hexavalent uranium (U(VI)) owing to its strong complexation ability with U(VI). However, the effect of DIC on U(VI) sorption on illite, which is a critical component of argillaceous rocks, is still unclear. In this study, we investigated the sorption of U(VI) on conditioned illite du Puy with varying DIC concentrations (up to 250 mM DIC) as a function of pH through batch sorption experiments, surface complexation modeling, and cryogenic time-resolved laser fluorescence spectroscopy (TRLFS). The distribution coefficients of U(VI) decreased with an increase in the DIC concentration. At relatively high DIC concentrations with respect to experimentally investigated range (≥100 mM DIC), no U(VI) sorption was observed. The U(VI) sorption on illite was modeled using the two-site protolysis non-electrostatic surface complexation and cation exchange model. Two ternary surface complexation reactions with carbonate were needed to depict the experimental sorption data in addition to binary and ternary hydroxo surface complexation reactions used to describe the U(VI) sorption to illite without carbonate. Cryogenic TRLFS data revealed that U(VI) did sorb to illite at high DIC concentrations (up to 10 mM DIC). The spectra were unchanged with varying DIC concentrations (2.0, 5.0, and 10 mM DIC) at pH ∼8.5, indicating that the surface speciation of U(VI) remained the same. The decay curves were biexponential, which further indicates that at least two surface species were responsible for the sorption. These results could improve the performance assessment of a deep geological disposal system in a sedimentary host rock.

Complexation of Nd(III)/Cm(III) with gluconate in alkaline NaCl and CaCl2 solutions: Solubility, TRLFS and DFT studies

The effect of gluconate on the solubility and aqueous speciation of An(III) and Ln(III) was studied using a combination of Nd(III) solubility experiments, Cm(III) time-resolved laser fluorescence spectroscopy (TRLFS) and density functional theory (DFT) calculations.Solubility experiments were performed under an Ar-atmosphere using a well-defined Nd(OH)3(s) solid phase equilibrated in NaCl (0.1–5.0 M) and CaCl2 (0.1–3.5 M) solutions with 9 ≤ pHc ≤ 13 and 10−6 M ≤ [GLU]tot ≤ 10−2 M. The solubility of Nd(OH)3(s) remains mostly unaffected in NaCl solutions with [GLU]tot = 10−3 M, whereas a clear increase in solubility is observed in dilute CaCl2 solutions with the same [GLU]tot and pHc ≥ 11. In concentrated CaCl2 solutions, gluconate does not affect the solubility of Nd(III) due to the competition with Ca–GLU complexes.Cm(III) TRLFS spectra collected in NaCl solutions with pHc ≈ 12 confirm the formation of weak Cm(III)–GLU complexes. The very strong red shift observed in dilute CaCl2 solutions in connection with high fluorescence intensities supports the formation of ternary Ca–Cm(III)–GLU complexes. The speciation of Cm(III) in 3.5 M CaCl2 solutions is mostly dominated by the complex Ca3[Cm(OH)6]3+, although the formation of ternary Ca–Cm(III)–GLU species is hinted at high gluconate concentrations. DFT calculations provide additional support to the formation of stable ternary Ca–Nd(III)–GLU aqueous complexes.This work provides key information to understand the chemical speciation and relevant equilibrium processes of An(III) and Ln(III) in the presence of gluconate under conditions relevant for nuclear waste disposal.

TRLFS study of hydrolyzed Eu(III) species

The hydrolysis of Eu(III) and Am(III) begins near neutral pH conditions, above which precipitation occurs due to low solubility. Careful sample characterization steps are a prerequisite for the speciation study of hydrolyzed Eu(III) complexes without the interference of colloidal particles or precipitation. Herein, the hydrolysis reaction of Eu(III) was studied using time-resolved laser fluorescence spectroscopy (TRLFS). Laser-induced breakdown detection was employed to monitor the presence of colloidal particles. The luminescence properties of Eu(III) and precipitated Eu(OH)3(s) were investigated and comparisons were made to those of aqua Eu3+. Parallel factor analysis was applied for the deconvolution of the TRLFS results. Both primary hydrolyzed Eu(III), EuOH2+ and precipitated Eu(OH)3(s) showed distinct luminescence spectral properties, including an enhanced hypersensitive luminescence peak (J = 2). An increased luminescence lifetime was observed for both EuOH2+ (τ = 130 ± 1 μs) and precipitated Eu(OH)3(s) (τ = 158 ± 7 μs) compared to that of aqua Eu3+ (τ = 112 ± 1 μs). A formation constant log*β1,1 of EuOH2+ at I = 0.1 M NaClO4 and 25 °C was measured to be –8.28 ± 0.22, which was converted to log*β°1,1 = –7.87 ± 0.22 at an infinitely diluted condition of I = 0 based on the specific ion interaction theory.

Sorption competition and kinetics of trivalent cations (Eu, Y and Cm) on corundum (α-Al2O3): A batch sorption and TRLFS study

In this study we have combined batch sorption and laser spectroscopic investigations to study the sorption of Eu(III) and Cm(III), on the aluminum oxide corundum in single- and multi-metal systems. Experiments were performed using a constant equilibrium time as a function of pH (pH-edges) or at constant pH as a function of equilibrium time (kinetic experiments) in 0.01 M NaClO4 and carbonate free conditions. The objective was to investigate how the sorption behavior of trivalent actinides and lanthanides is affected by the presence of another trivalent metal, Y(III). Our hypothesis was that the addition of higher concentrations of trivalent Y(III) together with a chemically similar trivalent metal, Eu(III) or Cm(III), would affect the sorption behavior of that metal. Batch experiments show that when the concentration of competing Y(III) is high enough (1 × 10−4 M) to occupy most of the surface sites, there is a clear shift in the position of the Eu(III) pH-edge to higher pH. Spectroscopic studies using time-resolved laser fluorescence spectroscopy (TRLFS) clearly confirm sorption competition between the trivalent metals Cm(III) and Y(III), but they also indicate a change in the surface speciation of the trivalent actinide in the presence of the competing metal if the concentration of that competing metal is high enough.

Time-Resolved Laser Fluorescence Spectroscopy Study of the Coordination Chemistry of a Hydrophilic CHON [1,2,3-Triazol-4-yl]pyridine Ligand with Cm(III) and Eu(III).

The complexation of Cm(III) and Eu(III) with the novel i-SANEX complexing agent 2,6-bis[1-(propan-1-ol)-1,2,3-triazol-4-yl]pyridine (PTD) was studied by time-resolved laser fluorescence spectroscopy (TRLFS). The formation of 1:3, 1:2, and 1:1 metal/ligand complexes was identified upon increasing PTD concentration in 10-3 mol/L HClO4 and in 0.44 mol/L HNO3 solutions. For all these complexes, stability constants were determined at different acid concentrations. Though under the extraction conditions proposed for an An/Ln separation process, that is, for 0.08 mol/L PTD in 0.44 mol/L HNO3, 1:3 complexes represent the major species, a significant fraction of 1:2 complexes was found. This is caused by ligand protonation, and results in lower Eu(III)/Am(III) separation factors compared to SO3-Ph-BTP, until now considered the i-SANEX reference ligand. Focused extraction studies performed at lower proton concentration, where the 1:3 complex is formed exclusively, confirm this assumption.

The Complexation of Cm(III) with Oxalate in Aqueous Solution at T = 20–90 °C: A Combined TRLFS and Quantum Chemical Study

The complexation of Cm(III) with oxalate is studied in aqueous solution as a function of the ligand concentration, the ionic strength (NaCl), and the temperature (T = 20–90 °C) by time-resolved laser fluorescence spectroscopy (TRLFS) and quantum chemical calculations. Four complex species ([Cm(Ox)n](3–2n), n = 1, 2, 3, 4) are identified, and their molar fractions are determined by peak deconvolution of the emission spectra. The conditional log K′n(T) values of the first three complexes are calculated and extrapolated to zero ionic strength with the specific ion interaction theory approach. The [Cm(Ox)4](5–) complex forms only at high temperatures. Thus, the log K4(0)(T) value was determined at T > 60 °C. The log K1(0)(25 °C) = 6.86 ± 0.02 decreases by 0.1 logarithmic units in the studied temperature range. The log K2(0)(25 °C) = 4.68 ± 0.09 increases by 0.35, and log K3(0)(25 °C) = 2.11 ± 0.05 increases by 0.37 orders of magnitude. The log Kn(0)(T) (n = 1, 2, 3) values are linearly correlated with the reciprocal temperature. Thus, their temperature dependencies are fitted with the linear Van’t Hoff equation yielding the standard reaction enthalpy (ΔrHm(0)) and standard reaction entropy (ΔrSm(0)) of the stepwise formation of the [Cm(Ox)n](3–2n) species (n = 1, 2, 3). Furthermore, the binary ion–ion interaction coefficients of the four Cm(III) oxalate species with Cl(–)/Na(+) are determined. The binding energies, bond lengths, and bond angles of the different Cm(III) oxalate complexes are calculated in the gas phase as well as in a box containing 1000 H2O molecules by ab inito calculations and molecular dynamics simulations, respectively.

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15N labeling and characterized by NMR and LIFDI-MS methods. 15N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP)3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP)3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

Interaction mechanism of Eu(III) with MX-80 bentonite studied by batch, TRLFS and kinetic desorption techniques

Speciation of surface adsorbed lanthanide/actinide ions at solid/water interface is very important for the evaluation of their physicochemical behavior in the natural environment. Herein, the sorption mechanism of Eu(III) on MX-80 bentonite is studied by batch sorption experiments, surface complexation modelling, time resolved laser fluorescence spectroscopy study (TRLFS) and kinetic dissociation measurements. The fluorescing adsorbed species are characterized with their emission spectra [the ratio of emission intensities of 5D0→7F1 (λ=594nm) and 5D0→7F2 (λ=619nm) transitions] and their fluorescence lifetime. The decrease of the intensity ratio points to the ongoing sorption/complexation with increasing pH. The increase of fluorescence lifetime with increasing pH indicates the changes from the formation of outer-sphere surface complexes to inner-sphere surface complexes. The species of adsorbed Eu(III) ions at bentonite surface are further demonstrated by surface complexation modeling, and the fitted results reveal that the sorption of Eu(III) on bentonite can be satisfactorily simulated by diffuse layer model with the strong and weak sites. The kinetic dissociation results of surface adsorbed Eu(III) from bentonite using chelating resin indicate that two different Eu–bentonite species (i.e., irreversible and reversible species) are required to explain the kinetic desorption results. The Eu species moves from the reversible to irreversible species with increasing pH values. The results are crucial to understand the physicochemical behavior of lanthanides in the natural environment.

A spectroscopic study on U(VI) biomineralization in cultivated Pseudomonas fluorescens biofilms isolated from granitic aquifers.

The interaction between the Pseudomonas fluorescens biofilm and U(VI) were studied using extended X-ray absorption fine structure spectroscopy (EXAFS), and time-resolved laser fluorescence spectroscopy (TRLFS). In EXAFS studies, the formation of a stable uranyl phosphate mineral, similar to autunite (Ca[UO2]2[PO4]2•2-6H2O) or meta-autunite (Ca[UO2]2[PO4]2•10-12H2O) was observed. This is the first time such a biomineralization process has been observed in P. fluorescens. Biomineralization occurs due to phosphate release from the cellular polyphosphate, likely as a cell's response to the added uranium. It differs significantly from the biosorption process occurring in the planktonic cells of the same strain. TRLFS studies of the uranium-contaminated nutrient medium identified aqueous Ca2UO2(CO3)3 and UO2(CO3)3 (4-) species, which in contrast to the biomineralization in the P. fluorescens biofilm, may contribute to the transport and migration of U(VI). The obtained results reveal that biofilms of P. fluorescens may play an important role in predicting the transport behavior of uranium in the environment. They will also contribute to the improvement of remediation methods in uranium-contaminated sites.

Immobilization of uranium in biofilm microorganisms exposed to groundwater seeps over granitic rock tunnel walls in Olkiluoto, Finland

In an underground rock characterization facility, the ONKALO tunnel in Finland, massive 5–10-mm thick biofilms were observed attached to tunnel walls where groundwater was seeping from bedrock fractures at a depth of 70m. In laboratory experiments performed in a flow cell with detached biofilms to study the effect of uranium on the biofilm, uranium was added to the circulating groundwater (CGW) obtained from the fracture feeding the biofilm. The final uranium concentration in the CGW was adjusted to 4.25×10−5M, in the range expected from a leaking spent nuclear fuel (SNF) canister in a future underground repository. The effects were investigated using microelectrodes to measure pH and Eh, time-resolved laser fluorescence spectroscopy (TRLFS), energy-filtered transmission electron microscopy (EF-TEM), and electron energy-loss spectroscopy (EELS) studies and thermodynamic calculations were utilized as well. The results indicated that the studied biofilms constituted their own microenvironments, which differed significantly from that of the CGW. A pH of 5.37 was recorded inside the biofilm, approximately 3.5units lower than the pH observed in the CGW, due to sulfide oxidation to sulfuric acid in the biofilm. Similarly, the Eh of +73mV inside the biofilm was approximately 420mV lower than the Eh measured in the CGW. Adding uranium increased the pH in the biofilm to 7.27 and reduced the Eh to −164mV. The changes of Eh and pH influenced the bioavailability of uranium, since microbial metabolic processes are sensitive to metals and their speciation. EF-TEM investigations indicated that uranium in the biofilm was immobilized intracellularly in microorganisms by the formation of metabolically mediated uranyl phosphate, similar to needle-shaped autunite (Ca[UO2]2[PO4]2·2–6H2O) or meta-autunite (Ca[UO2]2[PO4]2·10–12H2O). In contrast, TRLFS studies of the contaminated CGW identified aqueous uranium carbonate species, likely (Ca2UO2[CO3]3), formed due to the high concentration of carbonate in the CGW. The results agreed with thermodynamic calculations of the theoretically predominant field of uranium species, formed in the uranium-contaminated CGW at the measured geochemical parameters.This investigation clearly demonstrated that biological systems must be considered as a part of natural systems that can significantly influence radionuclide behavior. The results improve our understanding of the mechanisms of biofilm response to radionuclides in relation to safety assessments of SNF repositories.

Uptake of Eu(III) by 11 Å tobermorite and xonotlite: A TRLFS and EXAFS study

The uptake of Eu(III) by crystalline calcium silicate hydrate (C–S–H) phases 11 Å tobermorite and xonotlite has been investigated by the combined use of time-resolved laser fluorescence spectroscopy (TRLFS) and extended X-ray absorption fine structure (EXAFS) spectroscopy. Eu(III) doped tobermorite and xonotlite samples with varying metal loading (0.4, 7 and 35 μmol Eu/g solid phase) and reaction time (1–570 days) were investigated. The structural environment of Eu(III) taken up by tobermorite and xonotlite was found to depend on both parameters. At high Eu(III) loading (7 μmol Eu/g solid phase), TRLFS data indicated presence of three Eu(III) species with different fluorescence lifetimes after 1 day reaction time. The emission lifetimes deduced for the different species correspond to ∼4.7, ∼1 and 0 water molecules in the first coordination sphere, thus suggesting the presence of one surface species forming an inner-sphere surface complex and two species incorporated in the crystal structure. After longer contact times (90 days, 570 days), the surface species was not observed. At the lower Eu(III) loading (0.4 μmol Eu/g solid phase) and reaction times between 1 and 310 days only two Eu(III) species with ∼1–2 and 0 water molecules were detected, corresponding to Eu(III) being incorporated in the crystal structure. The results from EXAFS showed that the distances between Eu(III) and neighboring Ca and Si atoms in Eu(III) doped tobermorite increase after prolonged reaction time. Furthermore, the number of neighboring Ca and Si atoms was found to increase with time. This study demonstrates that binding into the structure of 11 Å tobermorite and xonotlite is the dominant mode of Eu(III) immobilization after long reaction time. This finding is essential for an overall assessment of the safe disposal of actinides in deep geological repositories for radioactive waste, as incorporation into the crystal structure suggests long-term immobilization in the repository environment.

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 Cm(III) with Fluoride in Aqueous Solution in the Temperature Range from 20 to 90 °C. A Joint TRLFS and Quantum Chemical Study

The formation of hydrated CmF2+ and CmF2+ species in aqueous solutions are studied in the temperature range of 20−90 °C at different fluoride concentrations and at constant ionic strength as well as at constant fluoride concentration and different ionic strengths by means of time-resolved laser fluorescence spectroscopy (TRLFS). The molar fractions of the Cm3+ aqua ion, CmF2+, and CmF2+ species are determined by peak deconvolution of the emission spectra. An increase of the mono- and difluoro complexes is observed with increasing fluoride concentration and/or increasing temperature. Using the specific ion interaction theory (SIT), the thermodynamic stability constants log K10 (CmF2+) and log K20 (CmF2+) as well as the values of Δε1 and Δε2 are determined as a function of temperature. The log K10 values increase from 3.56 ± 0.07 to 3.98 ± 0.06 and the log K20 values increase from 2.20 ± 0.84 to 3.34 ± 0.21 with increasing temperature from 20 to 90 °C. The value of Δε1 determined at 25 °C is in good agreement with literature data and shows a negligible temperature dependency in the studied temperature range. The value of Δε2 also shows only a moderate variation in the studied temperature range. The thermodynamic standard state data (ΔrHm0, ΔrSm0, ΔrGm0) are determined from the temperature dependence of the equilibrium constants at Im = 0 using the integrated Van’t Hoff equation. The fluorescence lifetime of the 6D′7/2(Cm3+) state is found to be constant at 63 ± 5 μs with increasing fluoride concentration. A model based on density functional theory (DFT) calculations is introduced to account for the additional quenching occurring through the near second sphere waters in the [Cm(H2O)8F]2+(H2O)18 complex.

A comparative batch sorption and time-resolved laser fluorescence spectroscopy study on the sorption of Eu(III) and Cm(III) on synthetic and natural kaolinite

AbstractEu(III) and Cm(III) sorption onto synthetic and natural kaolinite (St. Austell, UK) were studied by batch sorption experiments and time-resolved laser fluorescence spectroscopy (TRLFS). All investigations were performed under argon atmosphere (O2&lt;1 ppm). 0.1 M NaClO4and 0.25 g/L kaolinite were used as electrolyte and solid concentrations, respectively, throughout the study. Batch sorption experiments were performed with Eu(III), a homologue to trivalent actinides at three different metal ion concentrations between 6.6×10−8and 6.6×10−6 M. pH-dependent sorption was found to be congruent for the two lowest Eu(III) concentrations (6.6×10−8and 6.6×10−7 M) while a shift of the sorption distribution coefficient,Kd, to higher pH values was observed for the highest metal ion concentration (6.6×10−6 M). Furthermore, the natural kaolinite showed higher uptake of Eu(III) for the lowest metal ion concentration at pH&lt;5 as compared to the synthetic product. This difference is believed to arise from a higher amount of Eu(III) being sorbed as outer-sphere species on the natural kaolinite due to its negative surface charge being higher than that of the synthetic mineral. The spectroscopic investigations were performed with 2×10−7 M Cm(III) as a luminescent probe. Four single component spectra could be extracted from the recorded emission spectra for both the synthetic and the natural kaolinite, with peak positions in average at 598.8, 602.7, 607.4 and 611.0 nm. The three first emission peaks appearing between pH 5 and 13 were assigned to three inner-sphere Cm-complexes. The fourth emission peak appearing in the alkaline pH range (&gt;9) is assumed to be a result of Cm(III) incorporation by a surface precipitate of hitherto unknown composition.

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

Gd(III) and Cm(III) sorption onto a pure aluminum hydroxide, gibbsite ( α-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 6.4 × 10 −9 to 6.4 × 10 −5 M . pH-dependent sorption is found to be congruent at Gd(III) concentrations up to 6.4 × 10 −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 2 × 10 −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 μs, 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., γ-Al 2O 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.

TRLFS study on the complexation of Cm(III) with nitrate in the temperature range from 5 to 200 °C

The formation of aqueous Cm(III) nitrate complexes is studied in the temperature range from 5 to 200 °C by time resolved laser fluorescence spectroscopy (TRLFS). The experiments are performed in a custom build high pressure and high temperature fluorescence cell. The complex formation is measured at nitrate concentrations ranging from 0.10 to 4.61 mol/kg H2O. The mono- and dinitrate complexes are quantified by peak deconvolution of the fluorescence spectra and the complexation constants are determined as a function of the temperature. The conditional equilibrium constants are extrapolated to zero ionic strength using the specific ion interaction theory (SIT) and the thermodynamic standard state data (ΔrH°m, ΔrS°m, ΔrG°m, ΔrC°p,m) are determined from the temperature dependence of the equilibrium constants at I=0. The equilibrium constants up to 75 °C are well described by the Van´t Hoff equation (ΔrH°m independent of T and ΔrC°p,m=0). Modelling of the data at higher temperatures requires an extended equation including a term for the heat capacity changes (ΔrC°p,m).

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.

Sorption of Cm(III) onto different Feldspar surfaces: a TRLFS study

Summary The pH dependent sorption of Cm(III) onto alkali Feldspars (albite and orthoclase) is investigated by time resolved laser fluorescence spectroscopy (TRLFS) in the pH range from 3.4 to 9.4. Three single components are calculated from the raw spectra for both feldspar systems. The first component which corresponds to the Cm(III) aquo ion has a peak maximum at 593.8 nm and a fluorescence emission lifetime of 68±4 μs. This lifetime corresponds to a Cm(III) coordination of nine water molecules in the first coordination sphere of the actinide ion. The second component with a peak maximum at 601.4 nm corresponds to an adsorbed species. Its lifetime of 107±3 μs indicates a reduction of coordinating H2O/OH− ligands from nine to five caused by inner-sphere complex formation. The third component (603.6 nm) can be attributed to another sorption species. The corresponding lifetime is again 107±3 μs. Hence the number of coordinating ligands remains constant while the ligand field changes caused by the hydrolysis of the sorbed Cm(III). In a further set of experiments the Cm(III) sorption onto albite which is altered at pH 6.0 and pH 9.0 is also investigated by TRLFS. Independent of the dissolution and different surface morphologies caused by the alteration process the same Cm(III) species are formed as found for the sorption onto the untreated albite surface. With regard to the clarification of a feldspar dissolution mechanism the TRLFS results of the Cm(III) sorption onto altered feldspar surfaces give no evidence for a dissolution-reprecipitation based alteration mechanism.