Effect of neutralizing agent content on137Cs leaching from solidified boric acid waste products

For the preservation of environment from radioactive contamination, one of the properties necessary for solidified radioactive wastes is resistance to the release of radionuclides due to leaching by ground water after land disposal. In order to seek the optimum solidifying formulation for cement solidified boric acid concentrate from pressurized water reactor, a variety of specimens were prepared, varying the content of neutralizing agents and neutralization methods. For the leaching measurements, the ANS 16.1 Standard Leach Test was carried out for the specimens which had been mixed with small concentration of¹³⁷Cs to estimate the leachability index. According to our investigation, the optimum contents of neutralizing agents for neutralization of boric acid radioactive waste were determined in view of resistance ability to leaching. Eventually the leachability indices have turned out to be 5.807.91 depending on the formulations.     

Leaching behavior of137Cs in cement

To assess the safety of disposal of a radioactive waste-cement composite, the leaching of¹³⁷Cs from a waste composite into a surrounding fluid has been studied. Leaching tests were carried out in accordance with a method recommended by IAEA.¹ The leachability was measured as a function of bentonite clay to cement ratio. The fraction of¹³⁷-Cs leached from a specimen of Portland cement is 0.03–0.13 at a leaching time of 400 d. Results presented in this paper are examples of data obtained in a 10 y mortar and concrete testing project, which will influence the design of the engineered trench system for a future Yugoslav radioactive waste storage center.^2,3     

Leaching of uranium,radium and thorium from vertisol soil by ground water

Shallow land burial is routinely used for the disposal of low-level radioactive waste. Natural processes causing leaching of radionuclides can lead to contamination of surrounding ground water and soil by the radionuclides. The comparative leachability of radionuclides U_(nat), ²²⁶Ra, ²²⁸Ra and Th_(nat) from the soil of a radioactive waste disposal site, by ground water was evaluated. The probability of leaching was obtained in the following order Ra (≈77%) > U (≈40%) > Th (≈20%). Observed ratios (OR) were calculated to correlate leachability of radionuclides to that of major cations Ca²⁺ and Mg²⁺. The leaching of the radionuclides was seen to be dependent on Ca²⁺ and SO₄²⁻ leached from the soil. This study provides sitespecific leachability of radionuclides, that can be used as indicator of the tendency for migration or retention in soil. It can play an important role during an unforeseen accident like breach of containment at the waste disposal site leading to contamination of soil and ground water and causing hazard to public via drinking water route.     

Statistical estimate for evaluation of vitrified radioactive wastes

The evaluation of experimental results by methods of mathematical statistics enabled us to derive a number of conclusions on the leachability of vitrified radioactive wastes. Practical application of this procedure requires that the ratio of Na and K concentrations in the solution should be independent of the leaching time. The actual value of this ratio is influenced, above all, by the properties of the glass matrix. These results confirm the assumption that the Na/K correlation found could be extended for the determination of the Na/¹³⁷ Cs concentration ratio. This finding was used for the application of a In-In correlation, while evaluating the quality of vitrified radioactive wastes products.     

Comparative interpretation of leaching137Cs from radwaste sludge immobilized in cement

This paper presents results from studies made to determine the leachability of¹³⁷Cs from immobilized evaporator sludge from a Pressurized Water Reactor with cement. Leaching of¹³⁷Cs from cement matrix using three methods based on theoretical equations has been developed. These were: Method I, diffusion equation derived for a plane source model, Method II, rate equation for diffusion coupled with a first-order reaction. The leaching data were also analyzed by an empirical method employing a polynomial equation —Method III. Results presented in this paper are examples of data obtained in a cement testing project which will influence the design of a future radioactive waste storage center.     

A new standardized leaching test on stabilized wastes

A new long-term leaching test on stabilized and solidified waste material have been developed and standardized in the frame of the Standards, Measurements and Testing (SMT, formerly BCR) programme of the European Union (EU). The project was coordinated by Dr. H. A. Van der Sloot from ECN (Energy Research Foundation, The Netherlands). Twenty-five European laboratories from EU and EFTA countries participated in the intercomparison exercise. The solidification/stabilization treatment of municipal solid waste incinerator fly ashes, using cement as a matrix, was performed by INTRON B. V. (The Netherlands). The resulting solidified waste material was then used to produce the requested specimens for the intercomparison study. Before distribution to participants, specimen homogeneity was tested according to the state-of-the-art technology for physical-mechanical testing of cement samples as well as for consistency of chemical composition of the solid and stabilized waste. The results of tank leaching test for the above mentioned interlaboratory study are reported and the advantages of this new procedure for the study of the environmental impact of solidified wastes are discussed.     

Determination of the leaching rate of radionuclide 134Cs from the solidified radioactive wastes in Syrian Portland cement and cement–microsilica matrixes

The suitability of Syrian Portland cement for disposal of solidified low-level radioactive waste was assessed by measuring the leaching rate of ¹³⁴Cs. In ordinary cement concrete, a leaching rate of 1.309 × 10^?3 g/cm² per day was measured. Mixing this concrete with microsilica reduced significantly the leaching rate to 3.106 × 10^?4 g/cm² per day for 1% mixing, and to 9.645 × 10^?5 g/cm² per day for 3% mixing. It was also found that the application of a latex paint reduced these leaching rates by about 10%. These results, along with mechanical strength tests (under radiation exposure, high temperature, long water immersion and freeze–thaw cycling) indicate that Syrian Portland cement is suited for the disposal of low-level radioactive waste.     

Structural modifications in iron hydrated oxides induced by foreign cation

The aqueous radioactive wastes are complex chemical systems as consequence of the variety of the contained cations. The chemical systems precipitated from FeSO₄ and FeCl₃ simulating the aqueous radioactive waste treatment have been investigated by Mössbauer spectroscopy. Mg²⁺, Ca²⁺ and Ba²⁺ were used as foreign cations, the calcium being among the main components of aqueous radioactive waste. The results showed the ion radius influence varying from Mg²⁺ to Ba²⁺ in the case of the precipitation from FeSO₄. For the precipitation from ferric chloride the influences are not so evident.     

Leachability of toxic elements from solid wastes

We have examined the leachability of the toxic elements cadmium, arsenic, mercury, and selenium from solid wastes. The solid wastes studied are municipal incinerator ash, coal fly ash, hospital incinerator ash, raw sewage sludge, sewage incinerator bottom ash, and sewage incinerator lagoon ash (which is a combination of bottom and fly ashes). Cadmium displayed the greatest leachability in all waste types, with 76% leached from the municipal refuse incinerator ash. Although the sources of elements in the wastes are diverse, the leachability and hence the bioavailability in the incinerator ash appears mainly determined by the volatility of the element.     

Effect of curing time on immobilized Cs and Sr Isotopes leached from cement matrices

To assess the conditions for the safe disposal of radioactive wastes by encapsulation in cements, the effect of curing time on the leaching of radionuclides prior to the commencement of leaching experiments has been investigated. Leach tests were carried out on various cement matrices, using a modified IAEA method recommended by Hespe¹.     

Corrosion of simulated nuclear waste glass

Glasses are suitable host matrices for the immobilization of high-level radioactive wastes. The corrosion behaviour of nuclear waste glass in water is of considerable importance, since a potential route for returning of radionuclides to the biosphere is their leaching from the waste form into groundwater and subsequent transport by the groundwater to the surface. In this study, the preparation and characterization of borosilicate glasses of different chemical composition were investigated. Borosilicate glasses were doped with simulated nuclear waste oxides. The chemical corrosion in water of these glasses was followed by measuring the leach rates (g·cm^–2·day^–1), as a function of time. It was found that a simulated nuclear waste glass with the chemical composition (weight %), 15.61% Na₂O, 10.39% B₂O₃, 45.31% SiO₂, 13.42% ZnO, 6.61% TiO₂ and 8.66% waste oxides, is characterized by low melting temperature and with good corrosion resistance in water. Influence of passive layers on the leaching behaviour of nuclear waste glasses is discussed.     

Effect of curing time on the fraction of137Cs leached from cement matrix

To assess the safety of disposal of radioactive waste material in concrete, curing conditions and time of leaching radionuclide¹³⁷Cs have been studied. Leaching tests in concrete were carried out in accordance with a method recommended by IAEA¹.     

Trace metal and mineral speciation of remediated wastes using electron microscopy

Electron microscopic techniques, including scanning electron microscopy (SEM), transmission electron microscopy (TEM), and electron probe microanalyses (EPMA), were used to evaluate metal species and mineralogical phases associated with metal-bearing contaminated soil and industrial wastes that have been solidified and stabilized with Portland cement. Metals present in the wastes included arsenic, barium, cadmium, chromium, copper, lead, nickel, and zinc. In addition, mineral alterations and weathering features that affect the durability and containment of metals in aged remediated wastes were analyzed microscopically. Physical and chemical alteration processes identified included: freeze-thaw cracking; cracking caused by the formation of expansive minerals, such as ettringite and thaumasite; carbonation; and the movement of metals from waste aggregates into the surrounding cement matrix. Preliminary results show that although the extent of degradation after 6 years is considered slight to moderate, evaluations of durability and permanence of metals containment cannot be based on leaching and bulk chemistry analyses alone. The use of electron microscopic analyses is vital in studies that evaluate trace metal and mineral species and that attempt to predict the long-term performance of metal containment in solidified and stabilized wastes.     

Deposition of cesium and cobalt sorbed on zeolite in matrices of blast furnace slag

¹³⁷Cs and⁶⁰Co were sorbed from model solutions and waste water on chemically treated granular zeolite. The zeolite was incorporated into cement slurries based on blast furnace slag (BFS). The compressive and bending strength were measured after different times of hydration. The leaching tests were performed in water, base and acid solutions. The leachability was more pronounced only for samples in acidic solutions.     

Comparison of mathematical interpretation in radioactive waste leaching studies

Transport phenomena involved in the leaching of a radioactive material from a concrete composite matrix into surrounding water are investigated using three methods based on theoretical equations. These are: a diffusion equation derived for a plane source model, a rate equation for diffusion coupled with a first-order reaction and an empirical method employing a polynomial equation. The results are compared with respect to their applicability to the ¹³⁷Cs leaching data. The results presented in this paper are part of those obtained in a 25-year mortar and concrete testing project which will influence the design of radioactive waste management for a future Serbian radioactive waste disposal center.     

Effect of γ-dose on the crystal structure and leaching behavior of TiO<Subscript>2</Subscript> matrix labeled with <Superscript>181</Superscript>Hf/<Superscript>181</Superscript>Ta tracer

A new method for the possible incorporation of nuclear wastes has been attempted here by using ceramic matrix of TiO₂ as a host precursor for confinement. Hafnium is used as a simulant for actinide high-level waste. After incorporating ¹⁸¹Hf tracer into TiO₂ matrix, the leaching property of the resulting matrix was studied in water, sodium chloride and humic acid solutions. The leaching was measured in each of the case by following the radioactivity of ¹⁸¹Hf. TiO₂ matrix has also been exposed to γ-radiation in order to simulate the radiation field for nuclear waste. It has been investigated with a nuclear technique called time differential perturbed Angular Correlation (TDPAC) that the lattice structure of titania remains undisturbed even under a strong radiation field. The leaching of ¹⁸¹Hf has also been studied after irradiating the TiO₂ matrix with γ-radiation and the leaching behavior was observed not to change from that before irradiation.     

Magnesium-Potassium Phosphate Matrix for Immobilization of <Superscript>14</Superscript>C

Possibility of using a low-temperature magnesium-potassium phosphate matrix to solve the problem of immobilizing the radioactive wastes containing radioactive carbon (¹⁴C) in the form of calcium carbonate was examined. The physicochemical characteristics of the compounds obtained were determined. Large values of the ultimate compression strength (22 ± 5 MPa), which satisfy the technical requirements for cemented radioactive wastes (no less than 4.9 MPa), were obtained. The minimum carryover of carbon dioxide into the atmosphere in the course of synthesis and in keeping of samples for 14 days was noted: not more than 3 wt % relative to the starting CaCO₃. The leaching rate of carbonate ions from magnesium-potassium compounds by 28th day of contact with air does not exceed 10?9 g cm^?2 day^?1, with this value for the rest of the compound components not exceeding 10^?4 g cm^?2 day^?1. Thus, it was found that the magnesium?potassium phosphate matrix is an alternative to the cementation for solidification of radioactive wastes containing ¹⁴C.     

Synthetic calcium aluminosilicate monolith: V. Change in the pore structure in hydration and carbonization

The physicochemical properties of synthetic calcium aluminosilicate (SCAS) monoliths produced from fly ash, limestone, and sand in a three-stage process (filtration combustion with superadiabatic heating, fine grinding, and pressing) were studied. It was found that hydration and carbonization in a SCAS monolith during long hardening under natural (laboratory) conditions lead to perfection of the structure of pores, which improves its physicochemical properties. The presence of unreacted β-Ca₂SiO₄ in the SCAS monolith throughout the hardening period ensures its high immobilizing properties under the action of the hydrosphere on the matrix containing hazardous (including radioactive) wastes because of calcium hydrosilicate gel formation, which decreases the pore space volume. Examples were given for determining the dependence of the total rate of leaching of SCAS monoliths by deionized water at 90°C on the treatment time (MCC-1 test). The rate of leaching of a SCAS-MRW monolith (where MRW is model radioactive waste of closed nuclear fuel cycle) was found to be 6.7 × 10^?7, 7.2 × 10^?7, and 8.3 × 10^?7 g cm^?2 day^?1 at MRW contents of 10, 20, and 30 wt %, respectively. The possibility of integrated solutions of some environmental problems using energy- and resource-saving technologies was considered.     

Studies of leaching of copper ores and flotation wastes

In Poland, there are significant deposits of copper ores. During the copper extraction, large amounts of flotation wastes are produced. In the ores and flotation wastes many other important elements are present. The main goal of this work was analysis of uranium content and to elaborate procedures for recovery of U from these materials. Two types of ores and four types of waste were examined. It has been found that uranium content varies from 4.5 to 25 ppm. The other elements have also been determined in these materials: Cu (4–5 % in ores and 0.3–1.7 % in waste), Ag, Re, Mo, La, Ni, V, etc. For leaching, sulfuric acid and sodium carbonates of various concentrations (temperature, time) were used. The optimum conditions for leaching have been found. The concentration of uranium in the final solution was generally less than 25 μg/mL. The other elements are also present in the leaching solutions. Simultaneous liquid–liquid extraction of uranium with these elements from leaching solution is under study. In our opinion, only such combined procedure for the recovery of uranium together with the accompanying elements could be cost-effective.