0000000000056200
AUTHOR
Samer Amayri
Uptake of actinides by calcium silicate hydrate (C-S-H) phases
Abstract The sorption of actinides (Th, U – Am) was studied in dependence of the solid-to-liquid (S/L) ratio (0.5–20.0 g/L) and the calcium-to-silicon (C:S) ratio. The C:S ratio was varied between 1.80 and 0.70 to simulate the changing composition of the C-S-H phases during cement degradation from high to low C:S ratios. The decrease of the calcium content in the C-S-H phases by time is accompanied by a decrease in pH in the corresponding suspensions from 12.6 to 10.2. X-ray photoelectron spectroscopy (XPS) of the C-S-H phases showed an increasing depletion of Ca on the surface with increasing C:S ratio in comparison to the composition of the solid phase as a whole. The sorption experiments…
Neptunium(V) sorption on kaolinite
Abstract The sorption behavior of neptunium(V) onto the clay mineral kaolinite was studied in batch experiments under different experimental conditions: [Np(V)]=7 × 10−12–8 × 10−6 M, solid-to-liquid ratio 2–20 g L−1, I=0.1 and 0.01 M NaClO4, pH=6–10, ambient air and Ar atmosphere. The short-lived isotope 239Np (T 1/2=2.36 d) was used instead of 237Np (T 1/2=2.14 × 106 a) to study the sorption behavior of Np(V) at environmentally-relevant concentrations, i.e., 7 × 1012 M Np. In addition, 239Np(V) served as tracer to measure sorption isotherms over six orders of magnitude in Np concentration (4.8 × 10−12–1.0 × 10−4 M). The results show that Np(V) sorption on kaolinite is strongly influenced b…
Sorption of neptunium(V) on Opalinus Clay under aerobic/anaerobic conditions
Abstract The interaction between neptunium(V) and a natural argillaceous rock (Opalinus Clay (OPA), Mont Terri, Switzerland) has been investigated in batch sorption experiments by varying pH (6–10), Np(V) concentration (10−12–10−4 M), solid-to-liquid ratio (2–20 g/L), and partial pressure of CO2 (10−3.5 and 10−2.3 atm) under aerobic/anaerobic conditions in saturated calcite solution. All batch experiments were carried out using well characterized aerobic and anaerobic dry powders of OPA. The results show a great influence of pH on Np(V) sorption. Under aerobic conditions sorption increases with increasing pH until maximum sorption is reached between pH 8–9. At pH>9 sorption decreases due…
Mixed complexes of alkaline earth uranyl cabonates: A laser-induced time-resolved fluorescence spectroscopic study
The interaction of the alkaline earth ions Mg2+, Sr2+ and Ba2+ with the uranyl tricarbonate complex has been studied by time resolved laser-induced fluorescence spectroscopy. In contrast to the non-luminescent uranyl tricarbonate complex the formed products show slight luminescence properties. These have been used to determine the stoichiometry and complex stabilities of the formed compounds. As the alkaline earth elements are located in an outer shell of the complex the influence of the type of the alkaline earth element on the stability constant is not very drastic. Therefore all obtained data were averaged in order to derive an common stability constant for the described complexes. These…
Geochemical Interactions of Plutonium with Opalinus Clay Studied by Spatially Resolved Synchrotron Radiation Techniques
Plutonium plays an important role within nuclear waste materials because of its long half-life and high radiotoxicity. The aim of this study was to investigate with high spatial resolution the reactivity of the more oxidized forms of Pu(V,VI) within Opalinus Clay (OPA) rock, a heterogeneous, natural argillaceous rock considered as a potential repository host. A combination of synchrotron based X-ray microprobe and bulk techniques was used to study the spatial distribution and molecular speciation of Pu within OPA after diffusion and sorption processes. Microscopic chemical images revealed a pronounced impact of geochemical heterogeneities concerning the reactivity of the natural barrier mat…
Spectroscopic characterization of alkaline earth uranyl carbonates
A series of alkaline uranyl carbonates, M[UO{sub 2}(CO{sub 3}){sub 3}].nH{sub 2}O (M=Mg{sub 2}, Ca{sub 2}, Sr{sub 2}, Ba{sub 2}, Na{sub 2}Ca, and CaMg) was synthesized and characterized by inductively coupled plasma mass spectrometry (ICP-MS) and atomic absorption spectrometry (AAS) after nitric acid digestion, X-ray powder diffraction (XRD), and thermal analysis (TGA/DTA). The molecular structure of these compounds was characterized by extended X-ray absorption fine-structure (EXAFS) spectroscopy and X-ray photoelectron spectroscopy (XPS). Crystalline Ba{sub 2}[UO{sub 2}(CO{sub 3}){sub 3}].6H{sub 2}O was obtained for the first time. The EXAFS analysis showed that this compound consists of …
Neptunium(V) Sorption and Diffusion in Opalinus Clay
The sorption and diffusion behavior of 8 x 10(-6) M Np(V) in Opalinus Clay (OPA) with synthetic pore water (pH 7.6) as mobile phase was studied under ambient conditions by batch and diffusion experiments, respectively. The Kd value determined by batch experiments with OPA suspensions is equal to 0.025 +/- 0.005 m3/kg. The diffusion-accessible porosity epsilon of intact OPA as determined by through- and out-diffusion experiments with tritiated water (HTO) is equal to 0.15 +/- 0.01. The diffusion coefficient De and the rock capacity factor alpha of 22Na+ in OPA were measured by through-, out-, and in-diffusion experiments and asserted the reliability of these diffusion techniques. For the dif…
Determination of kinetic parameters of redox reactions using CE‐ICP‐MS: A case study for the reduction of Np(V) by hydroxylamine hydrochloride
The rate constants k of the reduction of 5 × 10-5 M Np(V) to Np(IV) by hydroxylamine hydrochloride (HAHCl) in 1 M HCl have been determined by CE-ICP-MS in the temperature range of ϑ = 30-70°C and with varying concentrations of HAHCl from 1 to 7.2 M. The reaction was found to have (pseudo)first order kinetics with respect to HAHCl. The experimental results for k ranged from 0.0029(1) min-1 (ϑ = 40°C, c(HAHCl) = 3 M) to 0.039(7) min-1 (ϑ = 60°C, c(HAHCl) = 7.2 M). The activation energy of the reaction was determined as EA = (72 ± 10) kJ/mol. These results and a comparison with literature data show that the coupling of CE to ICP-MS provides a powerful analytical tool for the investigation of…
Influence of humic acid on neptunium(V) sorption and diffusion in Opalinus Clay
SummaryThe influence of14C-labeled M42 humic acid (HA) on the interaction between neptunium(V) and natural clay rock (Opalinus Clay (OPA), Switzerland) has been investigated in batch sorption and diffusion experiments under ambient air conditions. The effect of 10 mg/L HA on the diffusion of 8 μM Np(V) in OPA has been investigated in synthetic OPA pore water (pH 7.6, I = 0.4M) for the first time. Batch sorption experiments as a function of solid-to-liquid ratio (4-20 g/L) were performed under same experimental conditions to compare distribution coefficients obtained from both diffusion and sorption experiments. These experiments showed only a slight influence of HA on Np(V) uptake by OPA in…
Modeling the sorption of Np(V) on Na-montmorillonite – effects of pH, ionic strength and CO2
Abstract Results from batch type experiments were modeled using the 2 SPNE SC/CE model developed by Bradbury and Baeyens. This work focused on the applicability of this model to the sorption of Np(V) on Na-montmorillonite under high saline conditions (0.1–3.0 M NaCl) in the pH range of 2–10 and in the presence of dissolved CO2 (p(CO2) = 10−3.3 atm). Under ambient air conditions two additional surface complexation species had to be taken into account, which are ternary species involving one carbonate ligand (≡SONpO2(CO3)2−, ≡SONpO2(CO3)Na−). The gained set of complexation parameters was successfully tested over a wide range of Np(V) concentrations (10−4 to 10−12 M) under Ar atmosphere and am…
Solubility and stability of liebigite, Ca2UO2(CO3)3·10H2O(cr), in dilute to concentrated NaCl and NaClO4 solutions at T = 22–80 °C
Abstract The solubility and thermodynamic stability of a synthetic liebigite was investigated in NaCl and NaClO4 solutions within a wide range of ionic strength (0.03 m ≤ Im ≤ 5.61 m), pH (7 ≤ pHm ≤ 9, with pHm = –log [H+]) and temperature (22 °C ≤ T ≤ 80 °C) conditions. A comprehensive characterization of the synthetic solid phase using XRD, quantitative chemical analysis, TG–DTA, SEM–EDS, IR and Raman spectroscopy confirmed the stoichiometry of Ca2UO2(CO3)3·10H2O(cr). At room temperature, liebigite remains stable and controls the solubility of U(VI) in the investigated NaCl and NaClO4 systems with Im ≤ 0.51 m. For the same temperature but high ionic strength (5.61 m NaCl), liebigite trans…
Investigation of the Electrophoretic Mobility of the Actinides Th, U, Np, Pu, and Am in Different Oxidation States.
The electrophoretic mobilities (μe) of the actinides Th and U-Am in different oxidation states (prepared in 1 M HCl and 1 M HClO4) have been determined by capillary electrophoresis (CE)-inductively coupled plasma mass spectrometry (ICPMS) using 1 M acetic acid as the background electrolyte, which has proven to provide an excellent setup for trace analysis at environmentally relevant concentrations (1 × 10-9 M). The values are independent of the respective acid solution. The μe of the Pu oxidation states +III to +VI have been measured. They agree with both the available literature data and the redox-stable analogues (Eu(III), Th(IV), Np(V), U(VI)) that have also been investigated. The trend …
Determination of the Stability Constants of the Acetate Complexes of the Actinides Am(III), Th(IV), Np(V), and U(VI) Using Capillary Electrophoresis-Inductively Coupled Plasma Mass Spectrometry.
Capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS) was used to determine the stability constants of the actinides Am(III), Th(IV), Np(V), and U(VI) at an ionic strength of I = 0.3 M. The obtained stability constants were extrapolated to zero ionic strength by means of the Davies equation. For both U(VI) and Am(III), three consecutive acetate complexes with log(β
Actinide Sorption Studies Using the Isotopes237Np and239Np
The sorption of Np(V) on γ-Al2O3 and the reference clay mineral kaolinite was studied in batch experiments in the presence and absence of ambient CO2 with 0.1 M NaClO4 as background electrolyte. The short-lived isotope 239Np (t1/2 = 2.36 d) was used instead of 237Np (t1/2 = 2.14 × 106 a) to study the sorption behaviour of Np(V) at environmentally-relevant concentrations, i.e., 7 pM Np. In addition, 239Np served as tracer to measure sorption isotherms over six orders of magnitude in neptunium concentration. γ-Al2O3 served as a reference for clay minerals like kaolinite to investigate the interaction of Np(V) with aluminol groups, which are crucial binding sites of clays.
Influence of temperature and background electrolyte on the sorption of neptunium(V) on Opalinus Clay
Abstract The temperature dependence of the sorption of 8 μM neptunium(V) on Opalinus Clay (OPA, Mont Terri, Switzerland) was investigated between 40 and 80 °C and compared to previous results for 20 °C. The batch experiments were performed under ambient air conditions in synthetic pore water (pH = 7.6, I = 0.4 M) under variation of the solid-to-liquid ratio between 2 and 20 g/L. Under these conditions the sorption of Np(V) on OPA was found to be an endothermic process as the average distribution coefficient (K d ) increases continuously with increasing temperature from 23 ± 4 L/kg at 40 °C to 678 ± 254 L/kg at 80 °C. In the temperature range of 40-80 °C, the plot of log(K d ) vs. 1/T could …
Speciation of neptunium during sorption and diffusion in natural clay
In argillaceous rocks, which are considered as a potential host rock for nuclear waste repositories, sorption and diffusion processes govern the migration behaviour of actinides like neptunium. For the safety analysis of such a repository, a molecular-level understanding of the transport and retardation phenomena of radioactive contaminants in the host rock is mandatory. The speciation of Np during sorption and diffusion in Opalinus Clay was studied at near neutral pH using a combination of spatially resolved synchrotron radiation techniques. During the sorption and diffusion experiments, the interaction of 8 μM Np(V) solutions with the clay lead to the formation of spots at the clay-water …