The report summarizes the results obtained by the Institute of Resource Ecology of the Helmholtz-Zentrum Dresden-Rossendorf within the BMWi-financed Joint Research Project “Geochemical retention of radionuclides on cement alteration phases (GRaZ)”. The project focused on the retention behavior of Ca-bentonite and cementitious material, both constituents of the geo-engineered barrier of deep geological repositories for high-level radioactive waste, towards radionuclides. Specifically, the influence of increased salinities and of hyperalkaline conditions on interaction processes in the system radionuclides – organics – clay/cementitious materials – aquifer was studied. For this purpose, complexation, sorption and desorption studies were performed at alkaline to hyperalkaline pH conditions (pH 8-13) and under variation of the ionic strength (0.1 to 4 M) applying complex solution compositions. For the U(VI) citrate system molecular structures dominating in the pH range 2-9 were studied spectroscopically (NMR, UV-Vis, FT-IR). As dominating species 2:2, 3:3, 3:2 and, above critical concentrations also 6:6 and 9:6 U(VI) citrate complexes were identified or confirmed and complex formation constants were determined. U(VI) sorption on Ca-bentonite at (hyper)alkaline conditions in mixed electrolyte solutions was studied by means of batch sorption experiments. The U(VI) retention on Ca-bentonite was shown to be very effective at pH>10, even in the presence of carbonate and despite the prevalence of anionic aqueous uranyl species. The presence of two independent U(VI) surface complexes on Ca-bentonite at pH 8-13 was shown by site-selective TRLFS and EXAFS spectroscopy. The sorption of anionic uranyl hydroxide complexes to the mineral surface was shown to be mediated by calcium cations. In further experiments, the effect of isosaccharinic acid (ISA) and polycarboxylate ether (PCE) on U(VI) and Eu(III) sorption, respectively, on Ca-bentonite was studied. An effect of ISA on U(VI) sorption on Ca-bentonite only occurs when ISA is present in very high excess to U(VI). The effect of PCE, as a commercial cement superplasticizer, on Eu(III) sorption onto Ca-bentonite was negligible already at moderate ionic strengths. The retention of U(VI) and Cm(III) by various C-(A-)S-H phases, representing different alteration stages of concrete, was studied by batch sorption experiments. Sorbed or incorporated actinide species were identified by TRLFS. The stability of U(VI) and Cm(III) doped C-(A-)S-H phases at high ionic strengths conditions was studied in solutions simulating the contact with North German claystone formation water. Potential changes of actinide speciation as well as formation of secondary phases due to leaching effects were followed spectroscopically. The results of this project show that both bentonite and cementitious material constitute an important retention barrier for actinides under hyperalkaline conditions and increased ionic strength.
| Identifer | oai:union.ndltd.org:DRESDEN/oai:qucosa:de:qucosa:75134 |
| Date | 23 June 2021 |
| Creators | Schmeide, Katja, Philipp, Thimo, Wolter, Jan-Martin, Kretzschmar, Jérôme, Dullies, Paul, Lippold, Holger, Schymura, Stefan, Stumpf, Thorsten |
| Source Sets | Hochschulschriftenserver (HSSS) der SLUB Dresden |
| Language | English |
| Detected Language | English |
| Type | doc-type:report, info:eu-repo/semantics/report, doc-type:Text |
| Rights | info:eu-repo/semantics/openAccess |
| Relation | urn:nbn:de:bsz:d120-qucosa-237182, qucosa:22349 |
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