Electrochemical behaviour of uranium (IV) in DMF at vitreous carbon

The electrochemical behaviour of UCl₄ (0.01 mol L⁻¹ up to 0.05 mol L⁻¹) in 0.1 mol L⁻¹ TBAPF₆/DMF solution at vitreous carbon was studied, at room temperature, by cyclic voltammetry and potentiostatic techniques. The electrolytic solutions were analyzed by UV spectroscopy (UV), and the electrodeposited films were characterized by Rutherford Backscattering Spectroscopy (RBS) and X-ray diffraction (XRD). The cyclic voltammetric results, at low UCl₄ concentrations (0.01 mol L⁻¹), point that the reduction of U(IV) to U(0) occurs in two steps involving mainly U(IV) and U(III) species. The first electron transfer reaction is quasi-reversible and the second irreversible. The diffusion coefficient of U(IV) in DMF and the charge rate constant were determined to be 4.78 × 10⁻⁷ cm² s⁻¹ and 1.93 × 10⁻³ cm s⁻¹ (at 0.02 V s⁻¹), respectively.RBS data obtained from samples prepared at constant potential (−3.10 V) during 3 h at room temperature, indicated the presence of uranium particles deposited all over the vitreous carbon surface with aggregates in some places, confirming that the second reduction step corresponds to uranium electrodeposition. No crystallographic ordering could be seen by XRD, pointing to an amorphous character of the uranium films.     

Chemical aspects of uranium recovery from seawater by amidoximated electron-beam-grafted polypropylene membranes

The amidoximated macroporous membranes (AO membranes) were prepared by post irradiation grafting of acrylonitrile (AN) onto thermally bonded non-woven matrix of poly(propylene) sheet using electron beams. These precursor membranes were reacted with hydroxylamine to convert AN to AO groups, and conditioned by treating them with 2.5% KOH at 80°C for 1 h. The water uptake capacity in seawater, Na⁺-exchange capacity, and uranium loading capacity from seawater of AO membranes were found to be 200±10 wt.%, (3.1±0.2)×10⁻⁴ mol/g, and (1.60±0.18)×10⁻³ mol/g, respectively. The expected functional group density based on the degree of AN grafting (125 wt.%) and its subsequent conversion to AO groups (80%) was found to be 7.8×10⁻³ mol/g. The comparison of the expected functional group density and uranium uptake capacity seems to suggest that UO₂²⁺ forms a complex with AO groups in 1:4 proportion. The uranium could be quantitatively desorbed (>90%) from the AO membrane in Na₂CO₃ and mineral acids like HCl in the equilibration times of 60 min and 40 min, respectively. Alkaline conditioning was found to be necessary for reuse of the membrane equilibrated with acid. However, AO membranes equilibrated with Na₂CO₃ could be reused without any conditioning for uranium sorption.     

Pt recovery using Cyphos IL-101 immobilized in biopolymer capsules

Cyphos^® IL-101, a tetraalkylphosphonium chloride salt (ionic liquid, IL) has been immobilized in capsules prepared by ionotropic gelation in calcium chloride solutions. The IL content was varied in the resin between 0.29 and 1.28 mmol IL g⁻¹. These resins have been tested for Pt recovery from HCl solutions. The equilibrium was very slightly affected by the concentration of HCl and chloride ions. The sorption isotherms were modeled using the Langmuir equation: the maximum sorption capacity was influenced by the drying of the resin but remained close to 177 mg Pt g⁻¹ for wet resin (i.e. 0.9 mmol Pt g⁻¹, dry weight basis, or 0.7 mol Pt mol⁻¹ Cyphos) and 142 mg Pt g⁻¹ for dry resin (i.e. 0.73 mmol Pt g⁻¹, or 0.57 mol Pt mol⁻¹ Cyphos). The presence of nitrates, nickel or copper ions (added under the form of chloride salts) did not significantly decrease sorption capacity even at concentrations as high as 5 g L⁻¹. Conversely, zinc at the concentration of 5 g L⁻¹, significantly decreased Pt sorption, probably due to the competition effect of chloro-anionic Zn species. This is another evidence of the ion exchange mechanism involved in the binding of hexachloroplatinate species. The kinetics are weakly affected by the agitation speed (in the range 150–350 rpm) indicating that the resistance to film diffusion is not the limiting step. The kinetics are affected by the IL content, metal concentration and more specifically the drying of the resin: intraparticle diffusion sounds to be the controlling kinetic step: the intraparticle diffusion coefficient varied between 2 × 10⁻¹² and 18 × 10⁻¹¹ m² min⁻¹, depending on experimental conditions. Platinum can be desorbed from loaded resin using either nitric acid (5 M) or thiourea (0.1 M in 0.1 M HCl acid solution). The resin was efficiently used for three sorption/desorption cycles using nitric acid: a decrease in sorption capacity and desorption efficiency was observed beginning with the third cycle, probably due to a progressive degradation of the resin.     

Solubilities of actinides in a domestic groundwater and a bentonite porewater calculated by using PHREEQC

This study presents the solubilities and speciations of actinides, calculated by the PHREEQC (V.2) code in a granitic groundwater and a Ca-bentonite porewater under a reducing condition. The respective solubilities for the amorphous U, Am, Th, Np and Pu compounds in the groundwater were 2.2 × 10⁻⁵, 1.2 × 10⁻⁷, 3.1 × 10⁻⁹, 3.4 × 10⁻⁹ and 6.3 × 10⁻¹¹ mole/L, and these values are comparable to the results calculated by the MUGREM and EQ3/6 codes. The major dissolved species for U, Am, Th, Np and Pu were UO₂(OH)₃⁻, Am(OH)₂⁺, Th(OH)₄(aq), Np(OH)₃CO₃⁻ and Pu(OH)₃CO₃⁻, respectively. However, carbonate complex ions were anticipated as the major species in the porewater except for thorium due to an increase of the carbonate concentration and a decrease of the pH.     

Development and applications of quaternary ammonium (QA) membrane electrodes in pharmaceutical preparation and in bioavailability of Prostaglandin E1 and Deoxycholate

The two novel ion-pairs (PB-TPB and NB-TPB) of quaternary ammonium drugs; propantheline bromide (PB), N,N-Diisopropyl-N-methyl-N-[2-(xanthen-9ylcarbonyloxy)ethyl] ammonium bromide and neostigmine bromide (NB), 3-(dimethylcarbamoyloxy) phenyl]-trimethylazanium have been synthesized, respectively and incorporated in poly (vinyl chloride)-based membrane electrodes for the quantification of propantheline bromide and neostigmine bromide in different pharmaceutical preparations. The influences of membrane compositions on the potentiometric responses of membrane electrodes have been found to substantially improve the performance characteristics. The best performance was reported with membranes having composition (w/w) of PB-TPB or NB-TPB (6%): PVC (34%): o-NPOE (60%). The proposed electrodes exhibit nernstian response in the concentration ranges of 2.1 × 10⁻⁷ M to 1.0 × 10⁻² M and 4.4 × 10⁻⁷ M to 1.0 × 10⁻² M with detection limit of 1.5 × 10⁻⁷ M and 3.3 × 10⁻⁷ M, respectively. Both the membrane electrodes perform satisfactorily over pH ranges of (3.5–7.5 and 4.0–7.0) with fast response times (11 s and 13 s), respectively. These drugs (PB and NB) were further utilized as different ion-pairs of Prostaglandin E₁ (PGE₁) and Deoxycholate (DOC) in poly (vinyl chloride)-based membrane electrodes for the determination of bioavailability of Prostaglandin E₁ and Deoxycholate in plasma of different patients.     

Kinetics and equilibrium of cesium sorption and desorption by particulate nuclear graphite

Data and a consistent physical and mathematical model for the kinetic and equilibrium sorptive behavior of cesium with a particulate, nuclear-grade graphite (H-451) is given. The most important conclusions are: (1) The kinetics of absorption and desorption of cesium by H-451 graphite in particulate form (size range 44–74μm) is such that, in general, several days are required to reach a near equilibrium state. Accordingly, the radiometric isopiestic method, although time consuming, appears to be the best method for obtaining equilibrium data in the cesium vapor pressure range of about 10 down to 10⁻⁴ Pa. (2) The kinetics data of the isopiestic experiment with graphite powder was found to be very well represented mathematically by an equation which is based on the site activation energy being approximately equal to the sorbate-sorbent site interaction energy, χ. In accordance with a theory for modified-exponential sorption which fits the equilibrium data well, the sites are taken to be non-uniformly distributed having a number which decreases exponentially with an interaction energy, χ, that has a finite upper limit χ_L.     

Voltammetric measurements of aminosalicylate drugs using bismuth film electrode

A bismuth film electrode (BiFE) prepared ex-situ on a supporting glassy carbon electrode exhibited convenient electroanalytical performance for voltammetric measurement of selected aminosalycilate drugs. The reduction behaviour of aminosalycilate drugs was studied in aqueous solutions within the pH range of 4–6. The voltammetric responses were compared with those obtained at the bare glassy carbon electrode under identical conditions. In the square-wave voltammetric operation mode the BiFE showed a linear response in the concentration range of 5 × 10⁻⁶ to 3.5 × 10⁻⁴ and 1 × 10⁻⁶ to 5 × 10⁻⁴ M for sulfasalazine and olsalazine, respectively. Its electrode surface revealed auspiciously high stability and remarkable reproducibility in the rapid analysis of aminosalycilate drugs. Finally, the BiFE was satisfactorily applied for direct quantitation of azo prodrugs in real pharmaceutical samples.     

Solid phase extraction of europium and uranium using Tulsion CH-90 resin

A procedure for the pre-concentration and separation of trace amounts of Eu and U by solid phase extraction using Tulsion CH-90 resin (with imino diacetate functional group) has been developed. The determinations of europium and uranium have been carried out by a radiotracer technique using ^152,154Eu and ²³³U radionuclides. The experiments were carried out using both batch and column techniques. Parameters such as equilibration rate, effect of pH, sorption and desorption of metal ions have been studied. The maximum sorption capacities for Eu and U were found to be 0.31 mmolg^–1 at pH 5.3 and 0.96 mmolg^–1 at pH 3.1 respectively.     

Electrodeposition of silver from the system AgNO3—ethyleneglycol—water. Effect of temperature ( −30°C) on the smoothness of silver deposits

The electrodeposition of silver from a nitrate bath can be improved by lowering the temperature and by the addition of ethyleneglycol as anti-freeze. When the bath temperature is lowered below 0°C, the dendritic silver deposition is suppressed and a smooth surface is obtained; at −30°C a very finegrained deposit results. The dendritic growth is supposedly prohibited partly by the lowering of temperature and to a less extent by the adsorption of ethyleneglycol at the surface both of which might enhance the activation overvoltage of silver deposition. From the polarisation measurement in, 0·25 M AgNO₃ electrolytes, the exchange current density of Ag deposition was evaluated as 1·70 × 10⁻² A/cm²(25°C) and with 50 vol. per cent ethyleneglycol, 9·72 × 10⁻⁴ A/cm² (25°C) and 1·22 × 10⁻⁵ A/cm² (−32°C). Adsorption of ethyleneglycol on Ag cathode was discussed by differential capacitance change.     

Long-term diffusion experiment at Mont Terri: first results from field and laboratory data

The diffusion of radionuclides is an important safety aspect for nuclear waste disposal in argillaceous host rocks. A long-term diffusion experiment, termed DI-A, is being carried out at the Mont Terri Rock Laboratory in the Opalinus Clay formation. The aim of this experiment is the understanding of the migration and sorption behaviour of cationic and anionic species in consolidated clays. This study reports on the experimental layout and the first results obtained from the DI-A experiment, which include the investigation of HTO, ²²Na⁺, Cs⁺, and I⁻ migration during a period of 1 year by analysing these tracers in the water circulating in the borehole. In addition, results obtained from through-diffusion experiments on small-sized samples with HTO, I⁻, and ³⁶Cl⁻ are presented.The decrease of tracer concentrations in the borehole is fastest for Cs⁺, followed by ²²Na⁺, HTO, and finally I⁻. The chemical composition of the artificial pore water in the borehole shows very little variation with time, thus indicating almost no chemical disturbance around the borehole.Through-diffusion experiments in the laboratory that were performed parallel to the bedding plane with two different methods yielded effective diffusion coefficients for HTO of 4–5×10⁻¹¹ m² s⁻¹ and significantly lower ones for anions Cl⁻ and I⁻ (0.7–1.6×10⁻¹¹ m² s⁻¹). The results indicate the importance of anion exclusion effects arising from the negatively charged clay surfaces. Furthermore, they demonstrate the anisotropic diffusion properties of the clay formation with significantly increased diffusion rates parallel to bedding relative to the perpendicular direction.The tracer data of the in situ experiment were successfully described with 2D diffusion models using diffusion and sorption parameters obtained from the above mentioned and other laboratory studies. The modelling results indicate that HTO and I⁻ diffused with no retardation. The retardation of Na⁺ and Cs⁺ could be described by empirical sorption expressions from previously derived batch sorption (Cs⁺) or diffusion (Na⁺) experiments.Overall, the obtained results demonstrate the feasibility of the technical concept to study the diffusion of non-sorbing and sorbing tracers in consolidated clays.     

Novel coated graphite electrode for the selective determination of Gd(III) in rocks and waste water samples

A novel gadolinium selective coated graphite electrode based on 2,6-bis-[1-{N-cyanopropyl,N-(2-methylpridyl)}aminoethyl]pyridine [P] is described. The best performance was exhibited by the electrode having membrane composition P:NaTPB:PVC:NPOE as 8:4:30:58 (%, w/w). The electrode demonstrates excellent potentiometric characteristics towards gadolinium ion over several interfering ions. The electrode exhibited a Nernstian response to Gd³⁺ ion over a wide concentration range 2.8 × 10⁻⁷ to 5.0 × 10⁻² M with a detection limit (6.3 ± 0.1) × 10⁻⁸ M and slope 19.6 ± 0.1 mV decade⁻¹ of a_Gd³⁺. Furthermore, it showed a fast response time (12 s) and can be used for 2.5 months without significant divergence in its characteristics. Noticeably, the electrode can tolerate the concentration of different surfactants up to 1.0 × 10⁻⁴ M and can be used successfully in 30% (v/v) ethanol media and 10% (v/v) methanol and acetonitrile water mixture. The useful pH range of this sensor is 2.0 to 8.0. It is sufficiently selective and can be used for the determination of Gd³⁺ ions in waste water and rock samples. It also serves as a good indicator in the potentiometric titration of GdCl₃ with EDTA.     

Amperometric detection of hydrogen peroxide at nano-nickel oxide/thionine and celestine blue nanocomposite-modified glassy carbon electrodes

A simple procedure was developed to prepare a glassy carbon (GC) electrode modified with nickel oxide (NiOx) nanoparticles and water-soluble dyes. By immersing the GC/NiOx modified electrode into thionine (TH) or celestine blue (CB) solutions for a short period of time (5–120 s), a thin film of the proposed molecules was immobilized onto the electrode surface. The modified electrodes showed stable and a well-defined redox couples at a wide pH range (2–12), with surface confined characteristics. In comparison to usual methods for the immobilization of dye molecules, such as electropolymerization or adsorption on the surface of preanodized electrodes, the electrochemical reversibility and stability of these modified electrodes have been improved. The surface coverage and heterogeneous electron transfer rate constants (k_s) of thionin and celestin blue immobilized on a NiOx-GC electrode were approximately 3.5 × 10⁻¹⁰ mol cm⁻², 6.12 s⁻¹, 5.9 × 10⁻¹⁰ mol cm⁻² and 6.58 s⁻¹, respectively. The results clearly show the high loading ability of the NiOx nanoparticles and great facilitation of the electron transfer between the immobilized TH, CB and NiOx nanoparticles. The modified electrodes show excellent electrocatalytic activity toward hydrogen peroxide reduction at a reduced overpotential. The catalytic rate constants for hydrogen peroxide reduction at GC/NiOx/CB and GC/NiOx/TH were 7.96 (±0.2) × 10³ M⁻¹ s⁻¹ and 5.5 (±0.2) × 10³ M⁻¹ s⁻¹, respectively. The detection limit, sensitivity and linear concentration range for hydrogen peroxide detection were 1.67 μM, 4.14 nA μM⁻¹ nA μM⁻¹ and 5 μM to 20 mM, and 0.36 μM, 7.62 nA μM⁻¹, and 1 μM to 10 mM for the GC/NiOx/TH and GC/NiOx/CB modified electrodes, respectively. Compared to other modified electrodes, these modified electrodes have many advantages, such as remarkable catalytic activity, good reproducibility, simple preparation procedures and long-term stabilities of signal responses during hydrogen peroxide reduction.     

Uptake-curves for the determination of diffusion coefficients and sorption equilibria for n-alkanes on zeolites

Sorption capacities and diffusion coefficients were measured for n-alkanes on a 5A-zeolite and ZSM-5 with a gravimetric setup. Significant heat effects were observed during the experimental determination of diffusion coefficients, which complicate the interpretation and the analysis of the experimental Uptake-curves. This effect depends significantly of the sorption rate, heat of adsorption and dissipation of heat. Taking into account these heat effects, reliable transport coefficients can be extracted. These agree well with diffusion coefficients obtained from other techniques, like PFG–NMR or ZLC. With the carbon chain-length the measured diffusivities decrease from 1.6 × 10⁻¹² to 0.5 × 10⁻¹² m²/s for propane to n-hexane for 5A-zeolite at 473 K. For n-butane and n-hexane values about 8 × 10⁻¹¹ and 4.6 × 10⁻¹¹ m²/s on MFI-type zeolites at 303 K are measured.From the equilibrium data, heats of adsorption were calculated and compared with literature data. The heat of adsorption for 5A-zeolite changes with the carbon chain-length from 32 to 44 kJ/mol for n-butane to n-octane, respectively. The heats of adsorption of alkanes on ZSM-5 were 60 kJ/mol for n-butane and 57 kJ/mol for hexane. Due to different adsorption sites in MFI-type zeolites two heats of adsorption were calculated for each alkane.     

Immobilization of horseradish peroxidase on self-assembled (3-mercaptopropyl)trimethoxysilane film: Characterization, direct electrochemistry, redox thermodynamics and biosensing

Highly organized (3-mercaptopropyl)trimethoxysilane (3-MPT) films have been prepared via self-assembled coupled with sol–gel linking technology. Horseradish peroxidase (HRP) is successfully immobilized onto the densely packed three-dimensional (3D) 3-MPT network and the direct electrochemistry of HRP is achieved without any electron mediators or promoters. Redox thermodynamics of HRP on the 3-MPT films, which is obtained from the temperature dependence of the reduction potential, suggests that the positive shift of redox potentials of HRP at the interface of 3-MPT originates from the solvent reorganization effects and conformational change of the polypeptide chain of HRP. Based on the direct electrochemistry and electrocatalytic ability of HRP, a sensitive third-generation amperometric H₂O₂ biosensor is developed with two linear dependence ranges of 5.0 × 10⁻⁷ to 1.0 × 10⁻⁴ and 1.0 × 10⁻⁴ to 2.0 × 10⁻² mol L⁻¹.     

DI-B experiment: planning, design and performance of an in situ diffusion experiment in the Opalinus Clay formation

The DI-B experiment is a long-term, natural-scale, in situ diffusion experiment, which is being performed in the Opalinus Clay formation at the Mont Terri Underground Rock Laboratory (URL), in Switzerland, employing nonradioactive tracers. One of the key aspects to be addressed for nuclear waste repository safety assessment purposes is the understanding of the transport mechanisms of the radionuclides contained in the radioactive waste. Consolidated clay formations display very low water hydraulic conductivities, so it is expected that the predominant transport process will be diffusion.The experimental set-up has been designed to withstand the site conditions and for monitoring and recording several physicochemical parameters (pH, conductivity, oxidation–reduction potential), as well as the pressures in the circuit and for the long-distance monitoring of the data acquisition system.The tracer selection has been made based on previous investigations carried out at CIEMAT, including a literature survey, laboratory sorption experiments and hydrogeochemical modeling for determining tracer stability under the physicochemical conditions to be expected in the site. The final selection includes ⁶Li, ⁸⁷Rb, D (as D₂O) and I (as I⁻). Hydrogeochemical modeling confirmed the stability of all the tracers selected. Batch sorption experiments showed that no sorption in the rock occurred in the case of ⁶Li, D and I (conservative tracers), whereas ⁸⁷Rb was 100% sorbed. However, ⁸⁷Rb was chosen because of its analogy with Cs, a relevant radionuclide commonly present in the nuclear spent fuel.Diffusion experiments have been carried out at laboratory scale with Opalinus Clay samples to provide diffusion parameters for modeling purposes. Effective diffusion coefficients, perpendicular and parallel to the bedding planes of the rock, respectively, were (1.68± 0.42)×10⁻¹¹ and (4.02± 0.30)×10⁻¹¹ m²/s for tritium, and (2.70± 0.27)×10⁻¹² and (1.38± 0.49)×10⁻¹¹ m²/s for iodide. Additional through-diffusion experiments (parallel to the bedding) were performed with the nonsorbing tracer ³⁶Cl⁻, in order to check the results obtained for iodide. The effective diffusion coefficient measured for chloride ions was (1.18± 0.27)×10⁻¹¹ m²/s, which is practically equal to the value obtained for iodide.Preliminary diffusion calculations have been carried out using two transport codes: GIMRT and CORE^2D, with conservative and nonconservative tracers, using effective diffusion coefficients (D_e) obtained experimentally in the laboratory (through-diffusion experiments) or selected from the literature. The diffusion profiles obtained from the calculations showed slight variations, which were consistent with the different modeling approaches employed. The predictive modeling results have been used to determine the initial tracer concentration that should be added to the circuit to assure well-defined profiles at the end of the experiment.This long-term in situ diffusion experiment will also provide useful data for the interpretation of previous diffusion experiments performed at the Mont Terri URL.     

Sawdust: A green and economical sorbent for thallium removal

Removal/preconcentration of thallium(I) ions from aqueous solution by sawdust; a waste material derived from the commercial processing of Cedrus Deodar wood for furniture production was investigated. A simple and low-cost modification results in increasing the sorption capacity of raw sawdust from 2.71 to 13.18 mg g⁻¹. Sorption was found to be rapid (98% within 8 min). The binding of metal ions was found to be pH dependent, optimal sorption accruing at around pH 6–9. Potentiometeric titrations of sawdust revealed two distinct pK_a values, the first having the value similar to carboxylic groups (3.3–4.8) and second comparable with that of amines (8.53–10.2) with the surface site densities of 1.99 × 10⁻⁴ and 7.94 × 10⁻⁵ mol g⁻¹, respectively. Retained Tl(I) ions were eluted with 5 ml 0.1 mol l⁻¹ HCl. Detection limit of 0.0125 μg ml⁻¹ was achieved with an enrichment factor of 160. Recovery was quantitative using sample volume of 800 ml. The Langmuir, Freundlich and D–R isotherm equations were used to describe partitioning behavior for the system at different temperatures. Kinetic and thermodynamic behavior of sawdust for Tl(I) ions removal was also studied.     

Application of silica gel as an effective modifier for the voltammetric determination of dopamine in the presence of ascorbic acid and uric acid

Amorphous silica gel modified carbon paste electrode (CPE) offers substantial improvements in voltammetric sensitivity and selectivity towards determination of dopamine (DA). Cyclic voltammetry of Fe(CN)₆^3−/4− as a negatively charged probe revealed that the surface of the silica gel modified carbon paste electrode had a high density of negative charge at pH 8.0. Therefore, the modified electrode adsorbed DA (pK_a = 8.9) and enhanced its voltammetric response while repulsed ascorbic acid (AA) (pK_a = 4.2) and uric acid (UA) (pK_a = 5.4) and inhibited their interfering effects. The influence of various experimental parameters including percent of silica gel in the CPE, pH of solution, and accumulation time and potentials, on the voltammetric response of DA was investigated. At the optimum conditions, the analytical curve was linear for dopamine concentrations from 2.0 × 10⁻⁷ to 1.0 × 10⁻⁶ mol L⁻¹ and 2.0 × 10⁻⁶ to 1.5 × 10⁻⁴ mol L⁻¹ with a detection limit (3σ) of 4.8 × 10⁻⁸ mol L⁻¹. The prepared electrode was used for determination of DA spiked into DA injection and human serum samples, and very good recovery results were obtained over a wide concentration range of DA.     

Poly (acridine orange) film modified electrode for the determination 1-naphthol in the presence of 2-naphthol

The voltammetric behavior of 1-naphthol was studied with a poly (acridine orange) (PAO) film modified glass carbon electrode (GCE). The electrooxidation of 1-naphthol was an irreversible process with its oxidation overpotential at the PAO electrode 180 mV lower than that on the GCE. PAO electrode demonstrated electrocatalytic activity to the electrooxidation of 1-naphthol giving a greatly improved detection limit down to 8 × 10⁻⁸ mol L⁻¹(S/N = 3). At the optimal experimental condition, the oxidation peak current from the PAO electrode was linearly proportional to the concentration of 1-naphthol in the range of 2 × 10⁻⁷ to 3.2 × 10⁻⁶ mol L⁻¹ and 5.2 × 10⁻⁶ to 1.2 × 10⁻⁴ mol L⁻¹. The differences of the oxidation peak potentials between 1-naphthol and the coexisted 2-naphthol was 170 mV allowing the selective detection of 1-naphthol in a mixed solution with 2-naphthol. The detection of 1-naphthol in tap water and river water was carried out with satisfactory results.     

The effect of bentonite on the interaction of I with PbO

In the long-term disposal of nuclear fuel waste, the radioactive fission product ¹²⁹I requires special attention. This is because of its long half-life (1.7·10⁷ yr), and the fact that it exists in solution as an anion (I⁻ or IO₃⁻) and does not intereact strongly with most geological materials such as clays and rock. Mixtures of bentonite and sand are being evaluated as candidate buffer materials to surround nuclear fuel waste containers in an underground disposal vault in Canada. Since bentonite and sand sorb only minor amounts of I⁻, research is being conducted to identify materials that could be mixed with the buffer material to selectively ‘sorb’ ¹²⁹I⁻, and consequently retard its movement through the buffer after the waste containers are breached. PbO has been proposed as a potential buffer additive, since it has been found to be very effective in removing I⁻ from solution. However, when bentonite is present (≥75 wt% of the total solids) in the PbO/I⁻ system, the amount of I⁻ removed from a solution with an initial I⁻ concentration of 10⁻⁵ mol/l is significantly decreased. On the other hand, kaolinite has little effect. The same phenomenon occurs when bentonite is physically separated from the PbO by a semipermeable membrane. In the PbO/I⁻ system, X-ray diffraction analysis indicates that the Pb phases present are PbO, Pb₃(CO₃)₂(OH)₂, and 7PbO·PbI₂·2H₂O; however, when bentonite is present, 7PbO·PbI₂·2H₂O is not detectable. When bentonite is treated with NaOAc to remove carbonates and then added to the Pb/I⁻ system, the amount of I⁻ released into solution is much less than in the system containing untreated bentonite. Furthermore, the addition of CaCO₃ or a solution of NaHCO₃ to the Pb/I⁻ system causes a release of I⁻ into solution. The data indicate that bentonite affects the stability of 7PbO·PbI₂·2H₂O, shifting the equilibrium between it and Pb₃(CO₃)₂(OH)₂ by increasing the HCO₃⁻ activity in the system (the bentonite contains 0.29% carbonate-C). The results indicate that PbO would not be an effective additive to a buffer material in a nuclear fuel waste disposal vault for the selective removal of ¹²⁹I⁻ from solution.     

Spatial variability of transport parameters in the Boom Clay

Several transport parameters (as hydraulic conductivity K, apparent diffusion coefficient D_p and diffusion accessible porosity η of HTO and iodide) have been intensively measured in the laboratory on high-quality cores taken at the Mol-1 borehole of the Mol site, in Belgium. The borehole was cored in 1997 from about 145 to 325 m depth, including the whole thickness of the Boom Formation, a Tertiary clay situated between 186 and 288 m depth (ground level), and part of the surrounding layers.The hydraulic conductivity measurements confirm the low permeability of the Boom Clay. An upper 90-m-thick clay layer within this formation can be considered as homogeneous with respect to the hydraulic conductivity. The vertical hydraulic conductivity K_v (i.e. K perpendicular to the bedding) is in the order of magnitude of 10⁻¹² m s⁻¹ and the average is 2.3×10⁻¹² m s⁻¹. This layer comprises from top to bottom the “Transition Zone”, the Putte Member, the Terhagen Member and the top of the Belsele-Waas Member of the Boom Formation. The 12 m at the base of the Formation, which corresponds to the lower part of the Belsele-Waas Member is characterised by larger K_v values (ranging between 10⁻¹¹ and 9×10⁻¹¹ m s⁻¹).The same thick clay layer can also be considered as homogeneous, regarding the values of the apparent diffusion coefficient and the diffusion accessible porosity η of tritiated water (HTO) and iodide. The average value of the diffusion accessible porosity is 0.37±0.03 for HTO and 0.16±0.02 for iodide. The apparent diffusion coefficient varies from 1.1×10⁻¹⁰ to 5.5×10⁻¹⁰ m² s⁻¹ for HTO and from 9.1×10⁻¹¹ to 5.2×10⁻¹⁰ m² s⁻¹ for iodide.