Separation of europium, cobalt and zinc on zirconium tungstate ion exchanger

Summary Amorphous zirconium tungstate inorganic ion-exchanger has been prepared under optimum conditions and characterized by IR, X-ray and thermal analysis. Surface area and capacity are determined. It has characteristic IR absorption peaks at 3242, 1628, 955, 868 and 432 cm^-1 and is thermally stable up to 450 °C. Its surface area was 16 m²/g with an exchange capacity of 0.541 meq/g. The sorption of radioactive europium from different media at ambient temperature by the zirconium tungstate (ZW) exchanger has been studied. The aim was to optimize the conditions for sorbing Eu from radioactive waste and cleaned the ZW from for recycling. The effect of contact time, metal concentration, pH and temperature has been measured. Percentual uptake of Eu(III) reaches 95% for HCl at pH 4 and increases with temperature indicating an endothermic sorption process. Uptake of Zn(II) and Co(II) on ZW from acetic acid was found to be 42% and 24% for cobalt and zinc, respectively. Desorption after saturation and the effect of other radioactive ions on the percentual uptake of Eu on ZW were investigated. A solution of 3M HCl releases 90%, 25% and 13% of the loaded Eu(III), Co(II) and Zn(II), respectively.     

Adsorption of cesium and strontium on natrified bentonites

The influence of chemical activation–natrification of bentonites on adsorption of Cs and Sr was studied with regards to utilization of bentonites for depositing high-level radioactive waste and spent nuclear fuel. Bentonite samples from three Slovak deposits in three different grain-size (15, 45 and 250 μm), natural and natrified forms (Na-bentonites); under various experimental conditions, such as contact time, adsorbent and adsorbate concentration have been studied. When comparing the Na-bentonites and their natural analogues, the highest adsorbed Cs and Sr amounts were reached on the natrified samples. After the Sr adsorption a drop in the pH equilibrium value was observed together with the increase of the initial Sr concentration. A disadvantage of the natrified bentonite forms is formation of colloid particles. After 2 h of phase mixing a gentle turbidity was observed as well as formation of a gel-like form. The above findings were confirmed by observing the particle distribution in dry and wet dispersion and centrifugation at two different speeds. Natrification as a technological process of bentonite quality improvement cannot be applied when constructing a long-term repository for high-level radioactive waste and spent nuclear fuel. The main problem of natrification is a technological process which leads to a significant pH increase. Alkaline environment in combination with the K presence and increased temperature in the vicinity of radio-active waste can lead to a rapid illitization of smectite and loss of the original adsorption qualities. Moreover, sodium additions are a significant point of uncertainty since it is not possible to state what amount of Na enters the interlayer space and what amount stays in the inter-partition space.     

Cesium sorption on bentonites and montmorillonite K10

The physical and chemical properties of illitic clay minerals from Slovak deposit suitable for application in engineering barriers for high level radioactive waste repositories and spent nuclear fuels were studied. The isolation of spent nuclear fuels and high level radioactive wastes from the outer environment in a deep repository is gained by means of a system of multiple engineering and natural sealing barriers. Vital segments in a multiple barrier system are clay rocks, of which bentonites represent the most suitable clay material. Cs-adsorption on fine fractions of adsorbents (bentonites from three Slovak deposits: Jelšovy potok J15, Kopernica K15, Lieskovec L15 and montmorillonite K10) has been studied with using batch of radiometric techniques. Adsorption parameters have been determined for adsorbent-cesium solution system as a function of contact time and adsorbate concentration. The influences of pH change, the effect of competitive cations, complex-forming organic chelating agents on the adsorption of Cs have also been studied.     

Sorption of cobalt(II) on soil: effects of birnessite and humic acid

To study the sorption behavior of Co(II) on soil and soil components such as birnessite, humic acid (HA) and their mixture, a series of experiment were conducted using the batch equilibrium technique on parameters such as equilibrium time, ionic strength, solution pH, and temperature. The soil samples collected from location near radioactive waste repository in Korea were used and birnessite was synthesized using a method by McKenzie for experiment. The experimental results indicate that Co sorption on soil, birnessite and soil with birnessite are strongly affected by the pH of solution. Typical for metal sorption to soils, the fraction of Co adsorbed increased as a function of pH at the experimental conditions. For sorption isotherm, the Freundlich equation provides a good fit for sorption on soil and soil with birnessite. Adsorption of HA on birnessite decreased with increase of pH, with a sharp decrease at pH 5?C6. From Co sorption experiment in a ternary system of Co, birnessite, and HA, the presence of HA enhanced Co adsorption at pH below 6.5 and reduced the Co sorption at the intermediate and high pH.     

Removal of cobalt from liquid radioactive waste by in situ electrochemical synthesis of ferrite

This study combined electrochemical synthesis with traditional ferrite method to remove Co²⁺ from simulated liquid radioactive waste (LRW). The experiment investigated the effects of various reaction conditions including current density, reaction time for electrosynthesis, reaction temperature, initial pH value and boric acid concentration as well as the type of power supply by measuring the concentration of Co²⁺ in the effluent, explored the reaction mechanism by measuring particles using XRD. The results showed that it was feasible to remove Co²⁺ from simulated LRW by electrochemical synthesis of ferrite. The best removal efficiency of 99.99% (the concentration of Co²⁺ in the effluent was 0.447 μg/L) was achieved under the optimal reaction conditions, the sediment was mainly composed of the mixture of CoFe₂O₄ and Fe₃O₄.     

Use of local soil for the decontamination of liquid radioactive wastes at PINSTECH

The use of locally available mineral clay for the removal of radionuclides from the low and intermediate level liquid waste has been studied. Adsorption behavior of this naturally available inorganic adsorbent is reported. The factors such as contact time, nature of the waste, pH and adsorption capacity have been considered. These optional physico-chemical conditions suggest an effective use of this locally available adsorbent for the decontamination of the liquid radioactive waste at Pakistan Institute of Nuclear Science and Technology (PINSTECH), Islamabad.     

Adsorption of Cr (VI) by treated weed <Emphasis Type="Italic">Salvinia cucullata</Emphasis>: kinetics and mechanism

In the present study a new low cost, easily available and environmentally friendly adsorbent was used for removal of Cr (VI). The Cr (VI) removal efficiency of the adsorbent was studied as a function of contact time, pH, adsorbent dose, adsorbate concentration, temperature and stirring speed. Different adsorption model equations for kinetics, isotherm and rate mechanism of the process were used to find the best model, which fit well to the experimental data. A full factorial design of n^k type was used to find a mathematical relation between the percentage of adsorption and variables affecting the adsorption process such as time, pH, adsorbate concentration and temperature. Using the Students ‘t’ test, the significance of each term of the derived equation was tested. The insignificant terms were removed from the derived equation. The adequacy of the equation after removing the insignificant terms was tested using the Fisher adequacy test. From the factorial design analysis it is found that pH has the most pronounced effect followed by time, temperature and the adsorbate concentration. A column study was performed using the optimum operating conditions.     

Analysis of 99Tc in the radioactive liquid waste after extraction into suitable solvent

⁹⁹Tc is one of the long lived fission product with high fission yield. From radioactive waste management point of view it is very much essential to evaluate the concentration of technetium in the radioactive liquid waste in order to finalise the treatment process to extract/isolate it from the stream which is discharged to the environment. For the estimation of ⁹⁹Tc in the radioactive liquid waste stream, extraction of the stable complex of technetium-tetraphenyl arsonium chloride (TPAC) into chloroform followed by beta counting was studied. Various parameters like pH, time of equilibration, concentration of TPAC in chloroform, use of other solvent for extraction as well as interference of various other radionuclides present in the waste were also studied. The radioactive liquid waste being handled in plant contains high concentrations of salts in the form of sodium nitrate. Hence effect of salt concentration on the percentage extraction was also evaluated. The extraction behavior does not dependent on change in the pH of the solution. Almost 99.5% extraction was observed in the pH range of 1?C13.0. High concentration of salt is affecting the extraction. However, this can be taken care by diluting the radioactive waste. It takes almost 90?min time for maximum extraction. Presence of radionuclides like ¹³⁷Cs, ⁹⁰Sr are not interfering the extraction of ⁹⁹Tc. However, ¹⁰⁶Ru is getting slightly extracted along with ⁹⁹Tc. The error due to ¹⁰⁶Ru can be eliminated by taking gamma spectrum and deducting the activity from the total beta activity to get ⁹⁹Tc activity. Nitrobenzene can be used for extraction of Tc?CTPAC complex in place of chloroform.     

Studies on adsorptive removal of radioactive cobalt from alkaline waste generated in sodium cooled fast breeder reactors

The removal of radioactive cobalt from alkaline waste containing sodium has been studied in batch process using two different inorganic compounds (a) hydrous manganese oxide (HMO), and (b) copper hexa-ferrocyanide (CFC) and compared with a strongly acidic cation exchange resin (Dowex50W×8). The percentage removal of cobalt was examined by varying experimental conditions, viz. pH of the solution, contact time and interfering ions. The studies showed that HMO can be used as an efficient adsorbent for the removal of cobalt from sodium containing wastes.     

Europium (III) and Uranium (VI) complexation by natural organic matter (NOM): Effect of source

For the safe long‐term storage of high‐level radioactive waste (HLW), detailed information about geo‐chemical behavior of radioactive and toxic metal ions under environmental conditions is important. Natural organic matter (NOM) can play a crucial role in the immobilization or mobilization of these metal ions due to its complexation and colloid formation tendency. In this study, the complexation of europium (as chemical homologue of trivalent actinides such as americium) and uranium (as main component of HLW) by ten humic acids (HA) from different sources and Suwannee NOM river extract has been analyzed. Capillary electrophoresis in combination with inductively coupled plasma mass spectrometry has been used for the evaluation of complex stability constants log β. In order to determine the complex stability constants a conservative single site model was used in this study. In dependence of their source and thus of NOM structure the log β values for the analyzed humic acids are in the range of 6.1–7.0 for Eu(III) and 5.2–6.4 for U(VI) (UO₂²⁺), respectively. In contrast to the results for HA the used Suwannee river NOM reveals log β values in the range of nearly two orders of magnitude lower (4.6 for Eu³⁺ and 4.5 for UO₂²⁺) under the geochemical conditions applied in this study.     

Extraction studies of trivalent ions from TALSPEAK medium using phsophonic acid-TBP solvent mixture

Indigenously synthesized extractant, phenyl (octyl) phosphonic acid (POPA) in tri-n-butylphosphate (TBP) and dodecane, has been investigated for the separation of americium from trivalent lanthanides in nitric acid medium as well as diethylene triaminepentaacetic acid (DTPA) and lactic acid mixture (TALSPEAK medium). Various experimental parameters like concentration of DTPA, lactic acid, TBP, nitrate ions and pH of the aqueous feed solution have been optimized to obtain the highest separation factor between americium and europium. Bulk actinide–lanthanide separation reagent, tetra (ethylhexyl) diglycolamide (TEHDGA), was equilibrated with simulated solution of americium and lanthanides, equivalent in concentration to the reprocessing waste originating from PHWR spent fuel. DTPA/lactic acid mixture was used to strip the metal ions from the loaded organic phase and re-extracted into POPA in TBP/dodecane to evaluate the separation factor of individual lanthanides with respect to americium. Very good separation factors between americium and trivalent lanthanides were obtained.     

Exploration of biomass waste as low cost adsorbents for removal of methylene blue dye: A review

Biomass waste, which is abundantly available has been studied as low cost biosorbent for dye sequestration from waste water. The present review reports on recent development for remediation of methylene blue dye by agricultural waste and fruit peel waste material. The aim of this study was to revise latest literature in the field of dye adsorption and discuss the dye adsorption capacity of different types of adsorbents. The activated carbon prepared from several types of biomass waste material enhances the adsorption efficiency after modification. The variety of activating agents, method of activation, characterization of biosorbent material like SEM, EDAX, BET surface area and FTIR analysis has been explored in the present review. The dye adsorption factors such as effect of pH, agitation time, temperature, adsorbate and adsorbent dose were discussed. The detailed investigation on applicability of isotherm model, kinetic model and thermodynamic parameters has also been presented. The adsorption kinetics and adsorption isotherm model focus on selectivity of adsorbent. Adsorption mechanism, Influence of surface area, influence of pH_pzc and comparative study of biomass waste adsorbent with other adsorbents have been carried out. The use of biomass waste adsorbents is economically feasible, environmental healthy and found to have outstanding removal capacity of dyes.     

Coating Carbon Nanotubes with Europium Oxide

Carbon nanotubes (CNTS) coating with europium oxide by a simple method is reported in this letter for the first time. The CNTS were refluxed in a solution of nitric acid containing europium nitrate, and the pH value was subsequently ajusted with ammonia solution. At last, the mixture was filtered and annealed. The TEM micrograph showed that the CNTS were covered with a uniform thin layer with thickness of about 15 nm. The XRD results revealed that the CNTS were coated with europium oxide.     

Multiplex immunoassays on size-categorized individual beads using time-resolved fluorescence

Miniaturized multiplex immunoassays were studied on individual beads to detect analytes in the same reaction mixture. With this approach hands-on time, cost, and amount of reagents as well as waste produced in the assays were reduced. Particles were categorized according to size for immunoassays of prostate specific antigen (PSA) and acute myocardial infarction (AMI) markers. Additionally, free and dual PSA assays were carried out on a single bead. The analyte concentration was detected directly on the surface of the beads using stable, intrinsically fluorescent europium and terbium chelates, and time-resolved fluorometry. Less than 0.4 ng ml⁻¹ PSA (corresponding to ca. 10 amol) was detected in free, dual and multiplex PSA assays and 0.1 and 2.4 ng ml⁻¹ of myoglobin (Mb) and creatine kinase MB (CK-MB), respectively, were monitored in the multiplex AMI marker assay. The effect of bead size and material on free PSA detection was also investigated. The beads were detected three times under different conditions; in liquid, after drying and after dissociating europium ions from the chelate into the DELFIA^® fluorescence enhancement solution. The same detection sensitivity was found for the dissociative and non-dissociative methods indicating that the current labeling technology for the surface detection is comparable to the commercial DELFIA system.     

Selective adsorption of cerium on activated charcoal from aqueous electrolyte solutions

The adsorption of cerium on activated charcoal has been studied as a function of shaking time, pH, concentration of adsorbate and temperature. The adsorption of cerium obeys Freyndlich and Langmuir isotherms. The influence of different cations and anions on cerium adsorption has been exmined. The adsorption of other metal ions on activated charcoal has been studied under specified conditions to check its selectivity for cerium adsorption. Consequently, cerium was removed from a mixture containing Ce, Ba, Sr, Ru, Cs, Cr, Nd, Pr and In. About 99% of the adsorbed cerium on activated charcoal can be recovered with 3M HNO₃ solution. A wavelelngth dispersive X-ray fluorescence spectrometer was used for measuring the cerium concentration.     

Solution Chemistry of Europium(III) Aqua Ion at Micromolar Concentrations as Probed by Direct Excitation Luminescence Spectroscopy

Direct excitation europium(III) luminescence spectroscopy is used to study the speciation of aqueous europium(III) ions at micromolar concentrations and near neutral pH. The pH and concentration dependence of the europium(III) ⁷F₀→⁵D₀ excitation peak is consistent with the formation of both mononuclear and dinuclear europium(III) hydroxide complexes at pH 6.5. Luminescence intensity and lifetime quenching studies in the presence of Nd^III at pH 5.0 and 6.5 support the formation of a dinuclear complex at pH 6.5. Steady state excitation and time‐resolved luminescence spectroscopy are consistent with the formation of innersphere nitrate and fluoride complexes, but outersphere perchlorate and chloride complexes at pH 6.5 and 5.0.     

Complexation of europium and uranium by humic acids analyzed by capillary electrophoresis-inductively coupled plasma mass spectrometry

Investigations of the mobility of radioactive and nonradioactive substances in the environment are important tasks for the development of a future disposal in deep geological formations. Dissolved organic matter (DOM) can play an important role in the mobilization of metal ions due to complexation. In this study, we investigate the complexation behavior of humic acid (HA) as a model substance for DOM and its influence on the migration of europium as homologue for the actinide americium and uranium as the principal component of nuclear fuel. As speciation technique, capillary electrophoresis (CE) was hyphenated with inductively coupled plasma mass spectrometry (ICP-MS). For the study, 0.5 mg·L?1 of the metals and 25 mg·L?1 of (purified Aldrich) HA and an aqueous solution sodium-perchlorate with an ionic strength of 10 mM at pH 5 were used. CE-ICP-MS clearly shows the different speciation of the triple positively charged europium and the double positively charged uranyl cation with HA.     

Adsorption of cesium on domestic bentonites

Bentonite is a natural clay and one of the most promising candidates for use as a buffer material in the geological disposal systems for spent nuclear fuel and high-level nuclear waste. It is intended to isolate metal canisters with highly radioactive waste products from the surrounding rocks because of its ability to retard the movement of radionuclides by adsorption. Slovak Republic avails of many significant deposits of bentonites. Adsorption of Cs on five Slovak bentonites of deposits (Jelšovy potok, Kopernica, Lieskovec, Lastovce and Dolná Ves) has been studied with the use of batch technique. In the case of Dolná Ves deposit, the mixed-layer illite–smectite has been identified as the main clay component. Natural and irradiated samples, in two different kinds of grain size: 45 and 250 μm have been used in the experiments. The adsorptions of Cs on bentonite under various experimental conditions, such as contact time, adsorbent and adsorbate concentrations have been studied. The Cation Exchange Capacity values for particular deposits drop in the following order: Jelšovy potok > Kopernica > Lieskovec > Lastovce > Dolná Ves. Bentonites irradiated samples with 390 kGy have shown higher specific surface and higher values of the adsorption capacity. Distribution coefficients have been determined for bentonite-cesium solution system as a function of contact time and adsorbate and adsorbent concentration. The data have been interpreted in terms of Langmuir isotherm. The uptake of Cs has been rapid and the adsorption of cesium has increased with increasing metal concentrations. The adsorption percentage has decreased with increasing of metal concentrations. Adsorption of Cs has been suppressed by presence of Ca²⁺ more than Na⁺ cation. Sorption experiments carried out show that the most suitable materials intended for use as barriers surrounding a canister of spent nuclear fuel are bentonites of the Jelšovy potok and Kopernica deposits.     

Sorption of europium on TiO2 and cement at high Ph in the presence of organic ligands

Summary Organic substances present in radioactive waste lower the sorption of metal ions at the high pH in cement matrices and, hence, enhance their possible migration. The aim of this study was to develop a method to compare organic substances or their degradation products with respect to what extent they affect metal sorption. Batch sorption studies were performed with cement or TiO₂ as solid phase and Eu(III) as a model element for trivalent lanthanides and actinides at pH 12.5 (representative of a cement waste matrix during the first approximately 100,000 years). Different kinds of ligands were studied in a broad concentration range, e.g., organic acids, cement additives, cleaning agents and degradation products from ion-exchange resin.     

Complexation studies with lanthanides and humic acid analyzed by ultrafiltration and capillary electrophoresis-inductively coupled plasma mass spectrometry

For the long-term storage of radioactive waste, detailed information about geo-chemical behavior of radioactive and toxic metal ions under environmental conditions is necessary. Humic acid (HA) can play an important role in the immobilisation or mobilisation of metal ions due to complexation and colloid formation. Therefore, we investigate the complexation behavior of HA and its influence on the migration or retardation of selected lanthanides (europium and gadolinium as homologues of the actinides americium and curium). Two independent speciation techniques, ultrafiltration and capillary electrophoresis coupled with inductively coupled plasma mass spectrometry (CE-ICP-MS) have been compared for the study of Eu and Gd interaction with (purified Aldrich) HA. The degree of complexation of Eu and Gd in 25 mg l(-1) Aldrich HA solutions was determined with a broad range of metal loading (Eu and Gd total concentration between 10(-6) and 10(-4) mol l(-1)), ionic strength of 10 mM (NaClO4) and different pH-values. From the CE-ICP-MS electropherograms, additional information on the charge of the Eu species was obtained by the use of 1-bromopropane as neutral marker. To detect HA in the ICP-MS and separate between HA complexed and non complexed metal ions in the CE-ICP-MS, we have halogenated the HA with iodine as ICP-MS marker.