Problems arising from uranium dispersion from mines and mine tailings, and the remediation of uranium contaminated areas, are discussed in this paper. In an experimental remediation study, a mixture of 70 vol.% of uraniferous mining wastes and 30 vol.% of a natural ceramic were used. The preliminary observations are discussed, and a model is proposed for the long term stabilization of mining tailings.
Observations and monitoring of contaminated sites carried out during the last 25 years have revealed local impacts of uranium on the environment in Lower Silesia, Poland. Uranium pollution is limited to waste dumps, mine tailings, and their close vicinities at Kowary Podgórze, Radoniów, Kopaniec and Kletno. Uranium dispersion takes place mechanically due to transport by river waters, chemically by rain and ground waters, and anthropogenically when the wastes are utilized in construction. Floods are an additional mechanism responsible for the mechanical dispersion of uranium. As a result of these uranium transport mechanisms, in order to minimize the impacts of uranium on the environment, the covering of dumps with non-radioactive material is suitable only for sites located away from populated areas.
Redox reactions have been observed at the Kowary tailings. During these reactions, iron hydroxide (goethite), hematite, and gypsum, are precipitated as solids. These observations provide a good prognosis for the long-term stabilization of radionuclides which can be incorporated into proposals for the construction of tailings sites. Using Eh-pH diagrams (system U-C-O-H, 25°C, 1 bar), UO2 is stable over the whole range of naturally occurring pHs, and is affected by Eh only in the range −0.4 to +0.1 volts in acidic environments, and below −0.4v in basal environments. BaSO4 and RaSO4 are stable under almost the same conditions as UO2. An environmentally significant redox boundary (FeS2 versus Fe2O3) occurs in the middle of the UO2 stability field. The geochemical and environmental behaviour of the elements discussed above suggest a mechanism for stabilizing radionuclides within stored wastes. The solidification of wastes should occur concurrently with naturally occurring redox reactions.
During oxidation, an active iron-hydroxide gel is produced. This gel is then dehydrated and converted into limonite (a mixed compound), a monohydrate (goethite), hydro-hematite (Fe2O3·1/2H2O) and hematite (Fe2O3). This reaction occurs in neutral or weakly acidic environments. A key problem in the proposed remediation project, therefore, is pH stabilization in order to maintain the required environment for oxidation and cementation reactions. In order to achieve such an environment and to stabilize the reactions, a construction method is proposed for new waste storage systems, based on mixed layers of waste and barrier components composed of natural materials. The presence of CaO or Ca(OH)2 and anhydrite in the proposed internal membrane will reduce the vertical migration of sulphates. Redox reactions will be responsible for the secondary precipitation (reduction) of uranyl. These same reactions occur naturally during the precipitation of uranium ores. Iron oxidation is the other process in the redox pair required to reduce [UO2]+2 to UO2. The resultant pitchblende is insoluble in normal oxidizing environments. To minimize the dissolution of UO2 by sulphuric acid generated during the iron oxidation reaction, the construction of pH active membranes containing calcium oxide or hydroxide are recommended. These compounds will react with the free acid to precipitate gypsum. Although several elements can be mobilized as a result of oxidation, radium remains in insoluble solid phases such as the common Ca, Ba and Sr sulphates.