Contact

Dr. Katja Schmeide
Surface Processes
k.schmeideAthzdr.de
Phone: +49 351 260 - 2436, 2513
Fax: +49 351 260 - 3553

Joint project: Retention of radionuclides relevant for final disposal in natural clay rock and saline systems – Subproject 2: Geochemical behavior and transport of radionuclides (Np, U, Pu and further radionuclides) in saline systems in the presence of repository-relevant organics


Financed by:
German Federal Ministry for Economic Affairs and Energy (BMWi) under Contract No. 02 E 10971
Funding period:
2011/07/01 – 2015/06/30
Cooperation Partners:
Johannes Gutenberg-Universität Mainz, Institut für Kernchemie
Karlsruher Institut für Technologie, Institut für Nukleare Entsorgung
Universität des Saarlandes, Anorganische Festkörperchemie
Technische Universität München, Fachgebiet Theoretische Chemie
Universität Potsdam, Institut für Chemie / Physikalische Chemie
Technische Universität Dresden, SG Strahlenschutz, Professur Radiochemie
Universität Heidelberg, Physikalisch-Chemisches Institut 
People:
Katja Schmeide (project leader), Holger Lippold, Johannes Kulenkampff, Norbert Jordan, Claudia Joseph, Henry Moll, Andrea Cherkouk
Students:
Katharina Fritsch, Maria Poetsch, Miriam Bader, Felix Spranger, Lisa Zehlike, Robert Gerasch, Lars Bittner, Jörg Schikora

Summary

Clay rock has been proposed as potential host rock for nuclear waste repositories in deep geological formations. Moreover, clay in form of bentonite is considered as buffer material in a variety of nuclear repository types.

Clay rock is closely associated with natural organic matter (e.g. low molecular weight organic acids such as acetate, propionate, lactate, and formate as well as fulvic and humic acid-like substances) that can be released from the clay under certain conditions. Generally, organic substances, occurring as dissolved species or as colloids in pore waters as well as attached to solids, can affect the mobility of radionuclides in the environment. Also microorganisms, that are indigenous in potential host rocks foreseen for nuclear waste disposal, are able to influence the speciation and therefore the mobility of actinides.

While ground and pore waters of South German clay deposits have ionic strengths below 0.5 M, the North German clay deposits are characterized by highly saline ground and pore waters with ionic strengths up to 4 M (Brewitz, 1982).

Therefore, the objective of this project was to study the influence of increased salinities on interaction processes in the system radionuclide – organics – clay – aquifer. To obtain information on the transport of actinides in clay formations in dependence on ionic strength and clay organics, complexation, sorption, diffusion and redox studies were performed under variation of the ionic strength (up to 4 M) and the background electrolyte (NaCl, CaCl2, MgCl2). For these studies a wide variety of spectroscopic methods was applied such as time-resolved laser-induced fluorescence spectroscopy (TRLFS), attenuated total reflection Fourier-transform infrared (ATR FT-IR) spectroscopy, X-ray absorption spectroscopy (XAS), and UV-vis spectroscopy combined with density functional theory (DFT) calculations. Surface complexation modeling for the interaction of U(VI) with montmorillonite (Fig. 1) was performed applying the two-site protolysis non electrostatic surface complexation and cation exchange (2SPNE SC/CE) model, developed by Bradbury and Baeyens (1997, 1999, 2002). Surface complexation constants were determined for the NaCl and CaCl2 system and were extrapolated to zero ionic strength. Applying these surface complexation constants, the surface complexation in mixed electrolytes could be modeled.

Fig. 1: U(VI) sorption on montmorillonite in NaCl medium. Left picture: batch sorption and surface complexation modeling in dependence on pH and ionic strength in absence (closed symbols) and presence (open symbols) of CO2. Right picture: ATR FT-IR study in dependence on ionic strength at pH 6.8 in absence of CO2.

Positron emission tomography (PET) could be established as a reliable measurement method for quantitative determination of heterogeneous diffusion coefficients in clays and for general tracer transport studies in barrier rocks. PET measurements were also conducted in order to display the improvement of the EDZ with waterglass injections. These experiments enable to draw conclusions on the complex reactive transport process and thus an estimation of the achieved improvement of the barrier function.

This research project was performed in collaboration with the R&D projects of the cooperation partners listed above. The results obtained within our subproject are summarized in:

Publications

Journal papers

  • Fritsch, K., Schmeide, K., Steudtner, R., Müller, K., Brendler, V., Stumpf, T.: Uranium(VI) sorption on montmorillonite at high ionic strengths: Surface complexation modelling in the NaCl and CaCl2 systems. Geochim. Cosmochim. Acta (2017, under review).
  • Lippold, H., Eidner, S., Kumke, M.U., Lippmann-Pipke, J.: Dynamics of metal-humate complexation equilibria as revealed by isotope exchange studies – a matter of concentration and time. Geochim. Cosmochim. Acta 197, 62-70 (2017).
  • Moll, H., Cherkouk, A., Bok, F., Bernhard, G.: Plutonium interaction studies with the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99: changes in the plutonium speciation by solvent extractions. Environ. Sci. Pollut. Res. 24, 13497-13508 (2017).
  • Bader, M., Müller, K., Foerstendorf, H., Drobot, B., Schmidt, M., Musat, N., Swanson, J.S., Reed, D.T., Stumpf, T., Cherkouk, A.: Multistage bioassociation of uranium onto an extremely halophilic archaeon revealed by a unique combination of spectroscopic and microscopic techniques. J. Hazard. Mat. 327, 225-232 (2017).
  • Kulenkampff, J., Gründig, M., Lippman-Pipke, J., Zakhnini, A.: Quantitative experimental monitoring of molecular diffusion in clay with positron emission tomography. Solid Earth 7, 1207-1215 (2016).
  • Kulenkampff, J., Gründig, M., Zakhnini, A., Lippmann-Pipke, J.: Geoscientific process monitoring with positron emission tomography (GeoPET). Solid Earth 7, 1217-1231 (2016).
  • Poetsch, M., Lippold, H.: Effects of ionic strength and fulvic acid on the adsorption of Tb3+ and Eu3+ onto clay. J. Contam. Hydrol. 192, 146-151 (2016).
  • Xiong, Q., Joseph, C., Schmeide, K., Jivkov, A.P.: Measurement and modelling of reactive transport in geological barriers for nuclear waste containment. Phys. Chem. Chem. Phys. 17, 30577-30589 (2015).
  • Moll, H., Lütke, L., Cherkouk, A.: Bacterial diversity in clay and actinide interactions with bacterial isolates in relation to nuclear waste disposal. In: Radionuclides in the Environment - Influence of chemical speciation and plant uptake on radionuclide migration. (Editoren: C. Walther, D. K. Gupta) Heidelberg, Springer Verlag (2015).
  • Moll, H., Lütke, L., Bachvarova, V., Cherkouk, A., Selenska-Pobell, S., Bernhard, G.: Interactions of the Mont Terri Opalinus Clay isolate Sporomusa sp. MT-2.99 with curium(III) and europium(III). Geomicrobiol. J. 31, 682-696 (2014).
  • Schmeide, K., Gürtler, S., Müller, K., Steudtner, R., Joseph, C., Bok, F., Brendler, V.: Interaction of U(VI) with Äspö diorite: A batch and in situ ATR FT-IR sorption study. Appl. Geochem. 49, 116-125 (2014).
  • Zakhnini, A., Kulenkampff, J., Sauerzapf, S., Pietrzyk, U., Lippmann-Pipke, J.: Monte Carlo simulations of GeoPET experiments: 3D images of tracer distributions (18F, 124I and 58Co) in Opalinus Clay, anhydrite and quartz. Computers & Geosciences 57, 183-196 (2013).

Ph.D. theses/Diploma theses/Bachelor theses

  • Gerasch, R.: Simulation und Parameterschätzung von 22Na-Diffusion in einem Opalinuston-Bohrkern mittels COMSOL Multiphysics und GeoPET-Datenabgleich. Master thesis, Brandenburgische Technische Universität Cottbus-Senftenberg (2015).
  • Spranger, F.: Immobilisierung von Tc(VII)/Tc(IV) an Eisenphasen. Bachelor thesis, Technische Universität Dresden (2015).
  • Bittner, L.: Prozessbeobachtung von Vergütungsmaßnahmen im Salzgestein mittels Positronen Emissions Tomographie (GeoPET). Diploma thesis, Hochschule Zittau/Görlitz (2014).
  • Joseph, C.: The ternary system U(VI) / humic acid / Opalinus Clay. Ph.D. thesis, Technische Universität Dresden (2013).
  • Zehlike, L.: Durchführung von Sorptions- und Desorptionsversuchen von U(VI) an Montmorillonit. Bachelor thesis, Technische Universität Dresden (2013).
  • Schikora, J.: Simulation von Diffusions-Adsorptionsprozessen in natürlichem Gesteinsmaterial mit COMSOL Multiphysics. Diploma thesis, Technische Universität Dresden (2012).

Talks

  • Kulenkampff, J., Gründig, M., Zakhnini, A., Schikora, J., Gerasch, R., Lippmann-Pipke, J.: Visualization of heterogeneous diffusion processes with PET aligned with 3D FE simulation results. 7th International Symposium on Process Tomography, 01.-03.09.2015, Dresden, Germany.
  • Fritsch, K., Schmeide, K.: U(VI) retention by montmorillonite at high salinities: Surface complexation modeling. International Workshop ABC-Salt (IV) - Actinide Brine Chemistry in a Salt-Based Repository. 14.-15.04.2015, Heidelberg, Germany.
  • Fritsch, K., Schmeide, K.: Montmorillonite as barrier material for uranium(VI) at high ionic strengths. 7th Mid-European Clay Conference, 16.-19.09.2014, Dresden, Germany.
  • Kulenkampff, J., Gründig, M., Zakhnini, A., Lippmann-Pipke, J.: Process tomography of diffusion with PET for evaluating anisotropy and heterogeneity. 7th Mid-European Clay Conference, 16.-19.09.2014, Dresden, Germany.
  • Gerasch, R., Kulenkampff, J., Lippmann-Pipke, J.: Parameter estimation of anisotropic diffusion in clay with COMSOL Multiphysics. COMSOL Conference 2014, 17.-19.09.2014, Cambridge, United Kingdom.
  • Moll, H., Lütke, L., Cherkouk, A., Bernhard, G.: Pu interaction with bacterial isolates from Mont Terri Opalinus Clay. Plutonium Futures - The Science 2014, 07.-12.09.2014, Las Vegas, USA.
  • Schmeide, K., Joseph, C., Brendler, V.: Uranium(VI) retention in clay and crystalline rock: How and why does it differ. 8th European Summer School on Separation Chemistry and Conditioning as well as Supramolecular, Intermolecular, Interaggregate Interactions, 07.-09.07.2014, Gustav-Stresemann-Institut, Bonn/Bad Godesberg, Germany.
  • Moll, H., Cherkouk, A.: Microorganisms and their impact on radionuclide speciation. 8th European Summer School on Separation Chemistry and Conditioning as well as Supramolecular, Intermolecular, Interaggregate Interactions, 07.-09.07.2014, Gustav-Stresemann-Institut, Bonn/Bad Godesberg, Germany.
  • Moll, H., Lütke, L., Cherkouk, A., Bernhard, G.: Actinide/Lanthanide interaction studies with a typical bacterial isolate from Mont Terri Opalinus Clay a potential host rock for nuclear waste disposal. IGD-TP Geodisposal 2014 Conference, 24.-26.06.2014, Manchester, United Kingdom.
  • Poetsch, M., Claus, M., Lippold, H.: Effect of ionic strength on the mobility of radionuclides in the presence of natural organic matter: Testing the Linear Additive Model. Goldschmidt Conference 2014, 08.-13.06.2014, Sacramento, USA.
  • Schmeide, K., Joseph, C., Fritsch, K.: Uranium(VI) and neptunium(V) retention by clay minerals and natural clay rock – Influence of clay organics, temperature and pore water salinity. 51st Annual Meeting of the Clay Minerals Society, 17.-21.05.2014, College Station, Texas, USA.
  • Schmeide, K., Joseph, C., Brendler, V.: U(VI) retention by potential host rocks: Comparison of clay and crystalline rock. RadChem 2014 - 17th Radiochemical Conference, 11.-16.05.2014, Mariánské Lázne, Czech Republic.
  • Moll, H., Lütke, L., Cherkouk, A., Bernhard, G.: Pu interaction studies with a typical bacterial isolate from Mont Terri Opalinus Clay. TD-246 Joint BN, GD, HT, MA Mont Terri Meeting, 10.-11.02.2014, St. Ursanne, Switzerland.
  • Bittner, L., Kulenkampff, J., Gründig, M., Lippmann-Pipke, J., Enzmann, F.: Direct observation of waterglass impregnation of fractured salt rock with positron emission tomography. International Conference on the Performance of Engineered Barriers: Backfill, Plugs & Seals, 06.-07.02.2014, Hannover, Germany.
  • Moll, H., Lütke, L., Cherkouk, A., Selenska-Pobell, S., Bernhard, G., Brendler, V.: Microbial influences on radionuclide behaviour – an example of less-understood problems and how to solve them. IGD-TP 4th Exchange Forum (EF4), 29.-30.10.2013, Prague, Czech Republic.
  • Wolf, M., Enzmann, F., Kulenkampff, J., Lippmann-Pipke, J.: 3D analysis of fluid flow in fissured salt rock. Migration’13 - 14th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 08.-13.09.2013, Brighton, United Kingdom.
  • Kulenkampff, J., Gründig, M., Korn, N., Zakhnini, A., Barth, T., Lippmann-Pipke, J.: Application of high-resolution positron-emission-tomography for quantitative spatiotemporal process monitoring in dense material. 7th World Congress on Industrial Process Tomography, 02.-05.09.2013, Krakow, Poland.
  • Fritsch, K., Schmeide, K.: Uranium(VI) sorption on montmorillonite in high ionic strength media. International Workshop ABC-Salt (III) - Actinide Brine Chemistry in a Salt-Based Repository. 15.-17.04.2013, Santa Fe, USA.
  • Kulenkampff, J., Gründig, M., Zakhnini, A., Lippmann-Pipke, J.: PET-Prozesstomographie von Transportvorgängen in Bohrkernen zur Verbesserung des Prozessverständnisses und zur Verifikation von Modellcodes. 73. Jahrestagung der Deutschen Geophysikalischen Gesellschaft, 04.-07.03.2013, Leipzig, Germany.
  • Joseph, C., van Loon, L. R., Jakob, A., Steudtner, R., Schmeide, K., Sachs, S., Bernhard, G.: Do elevated temperatures and organic matter influence the U(VI) diffusion through argillaceous rock? 5th International Meeting on "Clays in Natural and Engineered Barriers for Radioactive Waste Confinement", 22.-25.10.2012, Montpellier, France.
  • Kulenkampff, J., Gründig, M., Schikora, J., Zakhnini, A., Lippmann-Pipke, J.: Long-term spatiotemporal monitoring of diffusion processes in Opalinus drill cores with GeoPET and parameterization with COMSOL Multiphysics. 5th International Meeting on "Clays in Natural and Engineered Barriers for Radioactive Waste Confinement", 22.-25.10.2012, Montpellier, France.
  • Steudtner, R., Müller, K., Jäckel, E., Meyer, R., Schmeide, K., Günther, A.: Uranium chemistry in citric acid solution. 4th EuCheMS Chemistry Congress, 26.-30.08.2012, Prague, Czech Republic.
  • Lippold, H., Lippmann-Pipke, J.: Radiotracer studies on the kinetics and equilibrium characteristics of adsorption of humic matter. Goldschmidt 2012, 24.-29.06.2012, Montreal, Canada.
  • Zakhnini, A., Kulenkampff, J., Lippmann-Pipke, J., Pietrzyk, U.: GATE-based simulation in GeoSciences. OpenGATE collaboration meeting, 03.-04.05.2012, Athens, Greece.
  • Lippmann-Pipke, J., Kulenkampff, J., Gründig, M., Richter, M.: Matching 4D porous media fluid flow GeoPET data with COMSOL Multiphysics simulation results. COMSOL Multiphysics Konferenz, 26.-28.10.2011, Stuttgart/Ludwigburg, Germany.
  • Joseph, C., Van Loon, L.R., Jakob, A., Schmeide, K., Sachs, S., Bernhard, G.: Effect of temperature and humic acid on the U(VI) diffusion in compacted Opalinus Clay. 6th International Conference Uranium Mining and Hydrogeology (UMH VI), 18.-22.09.2011, Freiberg, Germany.

Poster

  • Moll, H., Cherkouk, A., Bernhard, G.: Interaction of anaerobic Mont Terri Opalinus Clay bacteria with plutonium(VI). Migration’15 - 15th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 13.-18.09.2015, Santa Fe, USA.
  • Lippold, H., Lippmann-Pipke, J.: Complexation of f-elements with humic carriers – how dynamic is the equilibrium? Migration’15 - 15th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 13.-18.09.2015, Santa Fe, USA.
  • Kulenkampff, J., Gründig, M., Zakhnini, A., Schikora, J., Gerasch, R., Lippmann-Pipke, J.: Visualization of heterogeneous diffusion processes with PET aligned with 3D FE simulation results. 7th International Symposium on Process Tomography, 01.-03.09.2015, Dresden, Germany.
  • Kulenkampff, J., Gründig, M., Lippmann-Pipke, J.: High-resolution Positron-Emission-Tomography for ultrasensitive spatio-temporal monitoring of tracer transport in porous media. 7th International Conference on Porous Media, 18.-21.05.2015, Padova, Italy.
  • Lippmann-Pipke, J., Kulenkampff, J., Lippold, H., Stuhlfauth, C., Gerasch, R., Gründig, M.: Benchmarking of reactive transport visualisation (PET) by numerical modelling with COMSOL Multiphysics and PhreeqC. 7th International Conference on Porous Media, 18.-21.05.2015, Padova, Italy.
  • Bader, M., Drobot, B., Müller, K., Stumpf, T., Cherkouk, A.: Biosorption of uranium on the cells of the halophilic archaea Halobacterium noricense DSM 15987 under highly saline conditions. International Workshop ABC-Salt (IV) - Actinide Brine Chemistry in a Salt-Based Repository. 14.-15.04.2015, Heidelberg, Germany.
  • Fritsch, K., Schmeide, K.: Uranium retention by montmorillonite at high ionic strengths. Clays in natural and engineered barriers for radioactive waste confinement, 23.-26.03.2015, Brussels, Belgium.
  • Lippmann-Pipke, J., Stuhlfauth, C., Lippold, H., Kulenkampff, J., Enzmann, F.: Aligning 1D and 2D axial symmetric transport simulations with observations: consequences for the reactive transport. International Symposium of the German Priority Programme SPP 1315 Biogeochemical Interfaces in Soil - Towards a Comprehensive and Mechanistic Understanding of Soil Functions, 06.-08.10.2014, Leipzig, Germany.
  • Fritsch, K., Schmeide, K.: Influence of ionic strength on U(VI) sorption onto montmorillonite at high salinities. 8th European Summer School on Separation Chemistry and Conditioning as well as Supramolecular, Intermolecular, Interaggregate Interactions, 07.-09.07.2014, Gustav-Stresemann-Institut, Bonn/Bad Godesberg, Germany.
  • Cherkouk, A., Lütke, L., Moll, H., Bachvarova, V., Selenska-Pobell, S., Bernhard, G.: Microorganisms in potential host rocks for geological disposal of nuclear waste and their interactions with uranium. IGD-TP Geodisposal 2014 Conference, 24.-26.06.2014, Manchester, United Kingdom.
  • Fritsch, K., Schmeide, K.: Effect of high ionic strengths on U(VI) retention in montmorillonite. RadChem 2014 - 17th Radiochemical Conference, 11.-16.05.2014, Mariánské Lázne, Czech Republic.
  • Fritsch, K., Schmeide, K., Bernhard, G.: Investigation of the mobility of uranium(VI) in argillaceous rock at higher salinity. Migration’13 - 14th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 08.-13.09.2013, Brighton, United Kingdom.
  • Lippold, H., Lippmann-Pipke, J.: Radiotracer exchange studies on the reversibility of interaction processes related to humic-bound metal transport. Migration’13 - 14th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 08.-13.09.2013, Brighton, United Kingdom.
  • Moll, H., Lütke, L., Bachvarova, V., Geissler, A., Selenska-Pobell, S., Bernhard, G.: Bacterial diversity in Mont Terri Opalinus Clay and the influence of the bacterial Sporomusa sp. isolate on plutonium speciation. Migration’13 - 14th International Conference on the Chemistry and Migration Behaviour of Actinides and Fission Products in the Geosphere, 08.-13.09.2013, Brighton, United Kingdom.
  • Schikora, J., Kulenkampff, J., Gründig, M., Lippmann-Pipke, J.: Modelling and simulation of 4D GeoPET measurements with COMSOL Multiphysics 4.2a. EGU General Assembly 2012, 22.-27.04.2012, Vienna, Austria.
  • Schmeide, K., Steudtner, R., Bernhard, G.: Formation of U(VI) lactate and citrate complexes and their sorption onto Opalinus Clay between 10 and 60°C. Workshop "HiTAC – High Temperature Aqueous Chemistry", 09.11.2011, Karlsruhe, Germany.
  • Kulenkampff, J., Enzmann, F., Gründig, M., Wolf, M., Lippold, H., Lippmann-Pipke, J.: Direct observation of preferential transport pathways in salt rocks by means of GeoPET. International Workshop ABC-Salt (II) - Actinide Brine Chemistry in a Salt-Based Repository. 07.-08.11.2011, Karlsruhe, Germany.
  • Zakhnini, A., Kulenkampff, J., Sauerzapf, S., Lippmann-Pipke, J., Pietrzyk, U.: Monte Carlo simulations of a ClearPET: Scatter and attenuation of gamma rays in various rock formations. 2011 IEEE Nuclear Science Symposium and Medical Imaging Conference, 23.-29.10.2011, Valencia, Spain.
  • Schmeide, K., Joseph, C., Steudtner, R., Bernhard, G.: Influence of organic ligands and temperature on U(VI) sorption and diffusion in the system Opalinus Clay/Opalinus Clay pore water. Migration’11 - 13th International Conference on the Chemistry and Migration Behavior of Actinides and Fission Products in the Geosphere, 18.-23.09.2011, Beijing, China.
  • Schmeide, K., Joseph, C., Bernhard, G.: Sorption and diffusion of U(VI) in the system Opalinus Clay/pore water in the absence and presence of organic ligands. NEA ClayClub Workshop "Clays under Nano- to Microscopic Resolution", 06.-08.09.2011, Karlsruhe, Germany.


Contact

Dr. Katja Schmeide
Surface Processes
k.schmeideAthzdr.de
Phone: +49 351 260 - 2436, 2513
Fax: +49 351 260 - 3553