Diffusion of 137Cs in compacted bentonite: Effect of pH and concentration

The effect of pH and concentration on the diffusion of ¹³⁷Cs in the compacted bentonite is studied with capillary method at the ionic strength of 0.1M NaClO₄. The apparent diffusion coefficient increases with increasing concentrations if the sorption of radionuclides is largely dependent on the radionuclide concentrations. The apparent diffusion coefficient decreases with increasing pH because most of the radionuclide sorption on the bentonite increases with increasing pH. The interlaminary space contributes significantly to the radionuclide diffusion and sorption in compacted bentonite. The relationship of the apparent diffusion coefficient and the effective diffusion coefficient of ¹³⁷Cs is also discussed.     

Diffusion of Re(VII) in gamma-irradiated bentonite: effect of compacted dry density and pH

Journal of Radioanalytical and Nuclear Chemistry - The temperature effect on the co-sequestration process receives little attention. Herein, kinetic and thermodynamic studies on the...     

Adsorption of La(III) onto GMZ bentonite: effect of contact time,bentonite content,pH value and ionic strength

Bentonite has been studied extensively because of its strong adsorption capacity. A local Na-bentonite named GMZ bentonite, collected from Gaomiaozi County (Inner Mongolia, China), was selected as the first choice of buffer/backfill material for the high-level radioactive waste repository in China. In this research, the adsorption of La (ΙΙΙ) onto GMZ bentonite was performed as a function of contact time, pH, solid content and metal ion concentrations by using the batch experiments. The results indicate that the adsorption of La (III) on GMZ bentonite achieves equilibration quickly and the kinetic adsorption follows the pseudo-second-order model; the adsorption of La (III) on the adsorbent is strongly dependent on pH and solid content, the adsorption process follows Langmuir isotherm. The equilibrium batch experiment data demonstrate that GMZ bentonite is effective adsorbent for the removal of La (III) from aqueous solution with the maximum adsorption capacity of 26.8 mg g⁻¹ under the given experimental conditions.     

Sorption of uranyl ions on silica: Effects of contact time, pH, ionic strength, concentration and phosphate

The sorption of UO₂ ²⁺ and phosphate on silica were simultaneously studied. The effect of contact time between the solid phase and aqueous solution, pH and ionic strength on the UO₂ ²⁺ sorption in the absence and the presence of phosphate was investigated. The effect of contact time between the solid phase and aqueous solution, pH and ionic strength on the phosphate sorption was investigated too. The isotherms of UO₂ ²⁺ and phosphate sorption at different pH values were determined. It was found that as compared with the sorption in the absence of phosphate, the sorption of UO₂ ²⁺ on silica in the presence of phosphate is increased at low pH and decreased at high pH; the abruptly increased with increasing pH in the pH range 3-6; the sorption is gradually decreased with increasing pH in the pH range 2-12; the sorption insensitive and the sorption of phosphate is sensitive to ionic strength.     

High-valent technetium complexes with the [(99)TcO(3)](+) core from in situ prepared mixed anhydrides of [(99)TcO(4)](-) and their reactivities

The highly reactive mixed anhydrides [TcO3(OCOPh)] and [TcO3(OBF3)]- were synthesized by treatment of [TcO4]- with strong Lewis acids benzoyl chloride and BF3.OEt2. These mixed anhydrides, prepared in situ, were used as precursors for the synthesis of complexes containing the [TcO3]+ core. Subsequent reactions with bi- or tridentate ligands resulted in new complexes comprised of the [TcO3]+ core. As examples with bidentate ligands, the classical complexes [TcO3Cl(bipy)] (1) (bipy = 2,2'-bipyridine) and [TcO3Cl(phen)] (2) (phen = 1,10-phenanthroline) have been prepared by this strategy and structurally characterized. The new compounds [TcO3(bpza)] (3) (bpza = di-1H-pyrazol-1-ylacetate), [TcO3(bpza*)] (4) (bpza* = bis(3,5-dimethyl-1H-pyrazol-1-yl)acetate), [TcO3(tpzm*)]+ (6) (tpzm* = 1,1,1-methanetriyltris(3,5-dimethyl-1H-pyrazole), and [ReO3(tpzm*)][ReO4] (7) are examples of complexes with tripod ligands. The complexes have been structurally characterized, and their 99Tc NMR spectra have been recorded. As a common feature, the X-ray structures show a distinct widening of the O-Tc-O angles, almost to a tetrahedral angle. With the perspective of radiopharmaceutical applications, water stability and reactivities toward alkenes are described.     

Diffusion of 3H, 99Tc, 125I, 36Cl and 85Sr in granite, concrete and bentonite

Understanding the characteristics of diffusion is essential in the assessment of radionuclide release through the backfill of waste repository. The diffusion behavior of ³H, ⁹⁹Tc, ¹²⁵I, ³⁶Cl and ⁸⁵Sr in granite, concrete and bentonite was studied in a specially designed diffusion cell. Diffusion coefficients (D, D _a) and time-lag (t _a) were measured, break-trough curves were plotted and experimental data were interpreted to predict diffusion rates. The results showed that tritium, iodine and chlorine could be considered as non-sorbing tracers, while technetium was weakly and strontium was strongly sorbed (no break-through was observed during the period of the experiments).     

Diffusion of Re(VII), Se(IV) and Cr(VI) in compacted GMZ bentonite

Journal of Radioanalytical and Nuclear Chemistry - The diffusion of Re(VII), Se(IV) and Cr(VI) in compacted Gaomiaozi bentonite was conducted by an integrated diffusion setup. The effective...     

Characterization of the reduction products of99TcO 4 − with stannous ions in citrate solutions

The chemical state of the products of⁹⁹TcO ₄ ⁻ reduction by Sn(II) in citrate media has been investigated using electrochemical methods. The Tc(V) chelates formed after consumption of one mole Sn(II)/g-atom TcO ₄ ⁻ were identified as oxo(biscitrato)technetates(V) existing in different coordination isomers. Their reduction products were hydroxo (biscitrato)technetates(IV). The products proved to be the same as reported in the case of the electrochemical reduction of TcO ₄ ⁻ in citric acid.     

Influence of contact time, pH, soil humic/fulvic acids, ionic strength and temperature on sorption of U(VI) onto MX-80 bentonite

The sorption of U(VI) from aqueous solution on MX-80 bentonite was studied as a function of contact time, pH, ionic strength, solid contents, humic acid (HA), fulvic acid (FA) and temperature under ambient conditions using batch technique. The results indicate that sorption of U(VI) on MX-80 bentonite is strongly dependent on pH and ionic strength. The removal of U(VI) to MX-80 bentonite is rather quick and the kinetic sorption data is simulated well by a pseudo-second-order rate equation. The presence of HA enhances the sorption of U(VI) on MX-80 bentonite obviously, but the influence of FA on U(VI) sorption is not obvious. The thermodynamic parameters (ΔH ⁰, ΔS ⁰, and ΔG ⁰) for the sorption of U(VI) calculated from temperature dependent sorption suggest that the sorption reaction is endothermic and spontaneous.     

A new experimental design to investigate the concentration dependent diffusion of Eu(III) in compacted bentonite

The 'in-diffusion method was used to study the diffusion behavior of Eu(III) in compacted bentonite. The results (K _d, apparent and effective diffusion coefficients) derived from the capillary method are in good agreement with the literature data for similar bentonite dry densities and similar radionuclide concentrations, and fits the Fick's second law very well. The method was used to study the effect of solution concentration (10^-7-10^-3 mol/l) on the diffusion and sorption behavior in compacted bentonite. The experiments were carried out in synthetic groundwater, at room temperature. The results suggested that the diffusion of Eu(III) in the bentonite was independent on the density of bentonite, but dependent on the solution concentration. In agreement to the literature, the K _d values from the capillary experiments are in most cases lower than those from batch experiments, they are about one-half to one-third the value to those from batch experiments. The difference between the K _dvalues from capillary and batch experiments are a strong function of the bulk density of the bentonite. The results suggest that the content of interlaminary space plays a very important role to the transport of Eu(III) in compacted bentonite.     

Diffusion of Re(VII) and Se (IV) in compacted GMZ bentonite in the presence of Bacillus spp.

Journal of Radioanalytical and Nuclear Chemistry - The effect of Bacillus spp. on Re(VII) and Se(IV) diffusion in compacted GMZ bentonite was investigated by a through-diffusion method. Bacillus...     

Preparation and characterization of [99TcO] apcitide: a technetium labeled peptide

[99mTcO] apcitide (99mTcO(P246)), the technetium complex of the 13 amino acid, apcitide, cyclo-(D-Tyr-Apc-Gly-Asp-Cys)-Gly-Gly-Cys(Acm)-Gly-Cys(Acm)-Gly-Gly-Cys-NH2, where Apc is L-[S-(3-aminopropyl)]cysteine (an arginine mimetic) and Acm is the acetamidomethyl protecting group, has high affinity and selectivity for the GPIIb/IIIa receptor that is expressed on the membrane surface of activated platelets and plays an integral role in platelet aggregation and thrombus formation. Bibapcitide, a 26 amino acid, bis-succinimidomethyl ether-linked dimer of the peptide apcitide has been formulated as a single-vial, lyophilized kit having the trade name AcuTect. When sterile, nonpyrogenic sodium pertechnetate (99mTcO4-) in 0.9% sodium chloride is added to the AcuTect radiopharmaceutical kit and the resulting kit is heated, [99mTcO] apcitide forms. This is the first radiopharmaceutical to target acute deep vein thrombosis (DVT) in the lower extremities. We report here the preparation, purification, and isolation of the 99Tc complex of apcitide and its characterization to determine the mode of binding of Tc to apcitide. [99TcO] apcitide was prepared, on the macroscopic level, by reaction of [99TcOCl4]- with apcitide, purified by preparative HPLC and isolated as a trifluoroacetate salt. [99TcO] apcitide can also be formed from the reaction of bibapcitide and 99TcO4- in the presence of Sn(II) and glucoheptonate at 80 degrees C, conditions that mimic the radiopharmaceutical kit preparation. FTIR data show a Tc=O stretch at 961.2 cm(-1), in the range observed for anionic [TcVO]3+ amide thiolate complexes. The mass spectral data is in agreement with the formula, [C51H73O20N17S5Tc]-, consistent with retention of Acm groups and the Tc binding in the Gly11-Gly12-Cys13 region of the peptide. Despite significant spectral overlap due to numerous similar amino acids, all protons of apcitide and [99TcO] apcitide were unambiguously assigned. The observation of two nonequivalent Acm groups and the observation of only 10 NH-CH cross-peaks in the TOCSY and COSY spectra of [99TcO] apcitide (NH-CH cross-peaks were absent for Gly11-Gly12-Cys13), compared to all 13 cross-peaks found in apcitide, provided compelling evidence to support the 99Tc binding to the terminal Gly11-Gly12-Cys13 region of apcitide.     

Sorption and desorption of radiostrontium on powdered bentonite: Effect of pH and fulvic acid

The effect of pH and fulvic acid on the sorption of Sr on bentonite was investigated by using batch experiments. The sorption and desorption isotherms of Sr on bentonite were determined at room temperature, at pH 6.0±0.2 and in presence of 0.1M NaCl. It was found that the sorption of Sr is independent at pH<8, and then increases slightly with increasing pH. Fulvic acid increases the sorption of Sr significantly on bentonite at low pH, but decreases the sorption of Sr at pH>8. The sorption of Sr on bentonite can be described by a reversible sorption process and the sorption mechanism consists mainly of ion exchange. This revised version was published online in July 2006 with corrections to the Cover Date.     

Effect of dry density on 125I diffusion in GMZ bentonite

Gaomiaozi(GMZ) bentonite is regarded as the favorable candidate backfilling material for a potential repository in China.It is important to understand the diffusion behavior of 125 I in GMZ bentonite and compare the diffusion behavior in GMZ and other types of bentonite like MX-80,Avonlea,etc.Therefore,through-and out-diffusion experiments were conducted to obtain the effective diffusion coefficient(D e) and distribution coefficient(K d).A computer code named Fitting for diffusion coefficient(FDP) was used for the experimental data processing and theoretical modeling.At the dry density of GMZ bentonite from 1600-2000 kg/m 3,the D e values of 125 I were(2.4-20.4) × 10-12 m 2 /s and K d values were constants.At dry density above 1800 kg/m 3,the diffusion behaviors were almost the same,indicating that the anion exclusion was ineffective.Out-diffusion results showed that the species of 125 I may be changed during the diffusion processing.It was probably caused by some organic matters or reducing substances in GMZ bentonite.Since the main composition of bentonite is montmorillonite,similar diffusion parameters were obtained in GMZ and other types of bentonite.The relationship of D e and accessible porosity(acc) could be described by Archie’s law with exponent n = 1.2-2.8 for 125 I diffusion in bentonite,whereas n = 2.0 in GMZ bentonite.Furthermore,bentonite with the dry density of 1800 kg/m 3 was proposed as the backfilling materials used in the construction of high level radioactivity waste repository.     

Th(IV) adsorption on alumina: effects of contact time, pH, ionic strength and phosphate

Adsorption of Th(IV) (total concentration, 10(-5)-10(-4) mol/L) was studied by a batch technique. The effects of pH, ionic strength, contact time, and phosphate on the adsorption of Th(IV) onto alumina were investigated. Adsorption isotherms of Th(IV) on alumina at approximately constant pH and three ionic strengths (0.05, 0.1, 0.5 mol/L KNO3) were determined. It was found that the pH values of aqueous solutions of both the Th(IV)-alumina and phosphate-alumina adsorption systems increase with increasing contact time, respectively. Adsorption of Th(IV) on alumina steeply increases with increasing pH from 1 to 4.5 and the adsorption edge consists of three regions. The phosphate added clearly enhances Th(IV) adsorption in the pH range 1-4. From the adsorption isotherms at approximately constant pH and three different ionic strengths, a reduced ionic strength effect was observed and is contradictory to the insensitive effect obtained from the adsorption edges on three oxides of Fe, Al, and Si at different ionic strengths. Compared with the adsorption edges at different ionic strengths, the adsorption isotherms at approximately constant pH and different ionic strengths are more advantageous in the investigation of ionic strength effect. The significantly positive effect of phosphate on Th(IV) adsorption onto alumina was attributed to strong surface binding of phosphate on alumina and the subsequent formation of ternary surface complexes involving Th(IV) and phosphate.     

Adsorption characteristics of Eu(III) on colloidal bentonite particles in aqueous solution: impact of colloid concentration,pH, foreign ions,and temperature

Journal of Radioanalytical and Nuclear Chemistry - The adsorption characteristics of Eu(III) on colloidal bentonite particles were investigated by batch experiments as functions of colloid...     

Effect of contact time,pH, humic acid and temperature on the sorption of radionuclide Am(III) onto attapulgite

Attapulgite has been applied in the sorption of metal and radionuclide ions since its discovery. Herein, radionuclide Am(III) sorption onto attapulgite was carried out at 25 °C in 0.01 mol/L NaNO₃ solutions. Effects of contact time, Am(III) initial concentration, pH, humic acid and temperature on Am(III) sorption onto attapulgite were investigated. The sorption of Am(III) increases with increasing contact time and reaches a maximum value within 24 h at different Am(III) initial concentration. The fast sorption velocity indicates that strong chemical sorption or strong surface complexation contributes to the sorption of Am(III) onto attapulgite under the experimental conditions. The experimental data can be described well by the pseudo-second-order rate model. The sorption of Am(III) onto attapulgite is strongly dependent on pH values and surface complexation is the main sorption mechanism. The presence of HA enhances the sorption of Am(III) onto attapulgite at pH < 8.5, whereas, at pH > 8.5, little effect of HA on Am(III) sorption is observed. The Langmuir, Freundlich and D-R models were used to simulate the sorption data at different pH values and the results indicated that Langmuir model simulates the experimental data better than Freundlich and D-R models. The thermodynamic parameters indicates that the sorption of Am(III) onto attapulgite is an endothermic and spontaneous process. The results suggest that the attapulgite is a suitable material as an adsorbent for preconcentration and immobilization of Am(III) from aqueous solutions.     

Effect of pH,foreign ions and temperature on radionickel sorption onto bentonite from Inner Mongolia,China

The development of nuclear power releases large amounts of radionuclides into the natural environment. Herein, the sorption of radionuclide ⁶³Ni on bentonite from Gaomiaozi county (Inner Mongolia, China) at different experimental conditions such as pH, contact time, ionic strength, foreign cations and anions, and temperatures were investigated by using batch technique. The results indicated that the sorption of ⁶³Ni on the bentonite was quickly at first contact time and then increased slowly with increasing contact time. The sorption of ⁶³Ni was strongly dependent on ionic strength at low pH values and independent of ionic strength at high pH values. The sorption of ⁶³Ni on bentonite was mainly dominated by outer-sphere surface complexation or ion exchange at low pH values, whereas inner-sphere surface complexation was the main sorption mechanism at high pH values. The Langmuir, Freundlich, and D–R models were applied to simulate the sorption isotherms of ⁶³Ni at three different temperatures, and the thermodynamic parameters (i.e., ΔH°, ΔS° and ΔG°) calculated from the temperature-dependent sorption isotherms indicated that the sorption of ⁶³Ni on bentonite was an endothermic and spontaneous process. Experimental results indicate that the bentonite is a suitable material for the preconcentration and solidification of ⁶³Ni from large volume of solutions in radionickel pollution cleanup.