TY - GEN A1 - Dettmann, Sophie A1 - Huittinen, Nina Maria A1 - Jahn, Nicolas A1 - Kretzschmar, Jerome A1 - Kumke, Michael A1 - Kutyma, Tamara A1 - Lohmann, Janik A1 - Reich, Tobias A1 - Schmeide, Katja A1 - Azzam, Salim Shams Aldin A1 - Spittler, Leon A1 - Stietz, Janina T1 - Influence of gluconate on the retention of Eu(III), Am(III), Th(IV), Pu(IV), and U(VI) by C-S-H (C/S = 0.8) T2 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe N2 - The retention of actinides in different oxidation states (An(X), X = III, IV, VI) by a calcium-silicate-hydrate (C-S-H) phase with a Ca/Si (C/S) ratio of 0.8 was investigated in the presence of gluconate (GLU). The actinides considered were Am(III), Th(IV), Pu(IV), and U(VI). Eu(III) was investigated as chemical analogue for Am(III) and Cm(III). In addition to the ternary systems An(X)/GLU/C-S-H, also binary systems An(X)/C-S-H, GLU/C-S-H, and An(X)/GLU were studied. Complementary analytical techniques were applied to address the different specific aspects of the binary and ternary systems. Time-resolved laser-induced luminescence spectroscopy (TRLFS) was applied in combination with parallel factor analysis (PARAFAC) to identify retained species and to monitor species-selective sorption kinetics. ¹³C and ²⁹Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied to determine the bulk structure and the composition of the C-S-H surface, respectively, in the absence and presence of GLU. The interaction of Th(IV) with GLU in different electrolytes was studied by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS). The influence of GLU on An(X) retention was investigated for a large concentration range up to 10⁻² M. The results showed that GLU had little to no effect on the overall An(X) retention by C-S-H with C/S of 0.8, regardless of the oxidation state of the actinides. For Eu(III), the TRLFS investigations additionally implied the formation of a Eu(III)-bearing precipitate with dissolved constituents of the C-S-H phase, which becomes structurally altered by the presence of GLU. For U(VI) sorption on the C-S-H phase, only a small influence of GLU could be established in the luminescence spectroscopic investigations, and no precipitation of U(VI)-containing secondary phases could be identified. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 1318 KW - actinide, organic ligand, sorption, cementitious material, concrete, luminescence KW - organic ligand KW - sorption KW - cementitious material KW - concrete KW - luminescence Y1 - 2023 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-588455 SN - 1866-8372 IS - 1318 ER - TY - JOUR A1 - Dettmann, Sophie A1 - Huittinen, Nina Maria A1 - Nicolas, Jahn A1 - Kretzschmar, Jerome A1 - Kumke, Michael A1 - Kutyma, Tamara A1 - Lohmann, Janik A1 - Reich, Tobias A1 - Schmeide, Katja A1 - Azzam, Salim Shams Aldin A1 - Spittler, Leon A1 - Stietz, Janina T1 - Influence of gluconate on the retention of Eu(III), Am(III), Th(IV), Pu(IV), and U(VI) by C-S-H (C/S = 0.8) JF - Frontiers in Nuclear Engineering N2 - The retention of actinides in different oxidation states (An(X), X = III, IV, VI) by a calcium-silicate-hydrate (C-S-H) phase with a Ca/Si (C/S) ratio of 0.8 was investigated in the presence of gluconate (GLU). The actinides considered were Am(III), Th(IV), Pu(IV), and U(VI). Eu(III) was investigated as chemical analogue for Am(III) and Cm(III). In addition to the ternary systems An(X)/GLU/C-S-H, also binary systems An(X)/C-S-H, GLU/C-S-H, and An(X)/GLU were studied. Complementary analytical techniques were applied to address the different specific aspects of the binary and ternary systems. Time-resolved laser-induced luminescence spectroscopy (TRLFS) was applied in combination with parallel factor analysis (PARAFAC) to identify retained species and to monitor species-selective sorption kinetics. ¹³C and ²⁹Si magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy and X-ray photoelectron spectroscopy (XPS) were applied to determine the bulk structure and the composition of the C-S-H surface, respectively, in the absence and presence of GLU. The interaction of Th(IV) with GLU in different electrolytes was studied by capillary electrophoresis-inductively coupled plasma mass spectrometry (CE-ICP-MS). The influence of GLU on An(X) retention was investigated for a large concentration range up to 10⁻² M. The results showed that GLU had little to no effect on the overall An(X) retention by C-S-H with C/S of 0.8, regardless of the oxidation state of the actinides. For Eu(III), the TRLFS investigations additionally implied the formation of a Eu(III)-bearing precipitate with dissolved constituents of the C-S-H phase, which becomes structurally altered by the presence of GLU. For U(VI) sorption on the C-S-H phase, only a small influence of GLU could be established in the luminescence spectroscopic investigations, and no precipitation of U(VI)-containing secondary phases could be identified. KW - actinide KW - organic ligand KW - sorption KW - cementitious material KW - concrete KW - luminescence Y1 - 2023 U6 - https://doi.org/10.3389/fnuen.2023.1124856 SN - 2813-3412 VL - 2 PB - Frontiers Media CY - Lausanne ER - TY - JOUR A1 - Kretzschmar, Jerome A1 - Haubitz, Toni A1 - Huebner, Rene A1 - Weiss, Stephan A1 - Husar, Richard A1 - Brendler, Vinzenz A1 - Stumpf, Thorsten T1 - Network-like arrangement of mixed-valence uranium oxide nanoparticles after glutathione-induced reduction of uranium(VI) JF - Chemical communications N2 - Glutathione (GSH), a ubiquitous intracellular reducing tripeptide, is able to reduce hexavalent uranium, U(VI), to its tetravalent form, U(IV), in aqueous media in vitro, inducing the formation of nanocrystalline mixed-valence uranium oxide particles. After the initial reduction to U(V) and subsequent dismutation, the yielded U(IV) rapidly hydrolyses under near-neutral conditions forming 2-5 nm sized nanoparticles. The latter further aggregate to 20-40 nm chain-like building blocks that finally arrange as network-like structures. Y1 - 2018 U6 - https://doi.org/10.1039/c8cc02070a SN - 1359-7345 SN - 1364-548X VL - 54 IS - 63 SP - 8697 EP - 8700 PB - Royal Society of Chemistry CY - Cambridge ER - TY - JOUR A1 - Müller, Katharina A1 - Foerstendorf, Harald A1 - Steudtner, Robin A1 - Tsushima, Satoru A1 - Kumke, Michael Uwe A1 - Lefèvre, Grégory A1 - Rothe, Jörg A1 - Mason, Harris A1 - Szabó, Zoltán A1 - Yang, Ping A1 - Adam, Christian K. R. A1 - André, Rémi A1 - Brennenstuhl, Katlen A1 - Chiorescu, Ion A1 - Cho, Herman M. A1 - Creff, Gaëlle A1 - Coppin, Frédéric A1 - Dardenne, Kathy A1 - Den Auwer, Christophe A1 - Drobot, Björn A1 - Eidner, Sascha A1 - Hess, Nancy J. A1 - Kaden, Peter A1 - Kremleva, Alena A1 - Kretzschmar, Jerome A1 - Krüger, Sven A1 - Platts, James A. A1 - Panak, Petra A1 - Polly, Robert A1 - Powell, Brian A. A1 - Rabung, Thomas A1 - Redon, Roland A1 - Reiller, Pascal E. A1 - Rösch, Notker A1 - Rossberg, André A1 - Scheinost, Andreas C. A1 - Schimmelpfennig, Bernd A1 - Schreckenbach, Georg A1 - Skerencak-Frech, Andrej A1 - Sladkov, Vladimir A1 - Solari, Pier Lorenzo A1 - Wang, Zheming A1 - Washton, Nancy M. A1 - Zhang, Xiaobin T1 - Interdisciplinary Round-Robin Test on molecular spectroscopy of the U(VI) Acetate System JF - ACS omega / American Chemical Society N2 - A comprehensive molecular analysis of a simple aqueous complexing system. U(VI) acetate. selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry. Y1 - 2019 U6 - https://doi.org/10.1021/acsomega.9b00164 SN - 2470-1343 VL - 4 IS - 5 SP - 8167 EP - 8177 PB - American Chemical Society CY - Washington ER - TY - JOUR A1 - Schott, Juliane A1 - Kretzschmar, Jerome A1 - Acker, Margret A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Drobot, Bjoern A1 - Barkleit, Astrid A1 - Taut, Steffen A1 - Brendler, Vinzenz A1 - Stumpf, Thorsten T1 - Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution JF - Dalton transactions : a journal of inorganic chemistry, including bioinorganic, organometallic, and solid-state chemistry N2 - In the presence of polyborates (detected by B-11-NMR) the formation of a weak Eu(III) borate complex (lg beta(11) similar to 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid. Y1 - 2014 U6 - https://doi.org/10.1039/c4dt00843j SN - 1477-9226 SN - 1477-9234 VL - 43 IS - 30 SP - 11516 EP - 11528 PB - Royal Society of Chemistry CY - Cambridge ER - TY - GEN A1 - Schott, Juliane A1 - Kretzschmar, Jerome A1 - Acker, Margret A1 - Eidner, Sascha A1 - Kumke, Michael Uwe A1 - Drobot, Björn A1 - Barkleit, Astrid A1 - Taut, Steffen A1 - Brendler, Vinzenz A1 - Stumpf, Thorsten T1 - Formation of a Eu(III) borate solid species from a weak Eu(III) borate complex in aqueous solution N2 - In the presence of polyborates (detected by 11B-NMR) the formation of a weak Eu(III) borate complex (lg β11 ∼ 2, estimated) was observed by time-resolved laser-induced fluorescence spectroscopy (TRLFS). This complex is a precursor for the formation of a solid Eu(III) borate species. The formation of this solid in solution was investigated by TRLFS as a function of the total boron concentration: the lower the total boron concentration, the slower is the solid formation. The solid Eu(III) borate was characterized by IR spectroscopy, powder XRD and solid-state TRLFS. The determination of the europium to boron ratio portends the existence of pentaborate units in the amorphous solid. T3 - Zweitveröffentlichungen der Universität Potsdam : Mathematisch-Naturwissenschaftliche Reihe - 277 Y1 - 2014 U6 - http://nbn-resolving.de/urn/resolver.pl?urn:nbn:de:kobv:517-opus4-98774 ER -