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Concrete widely serves as an engineering barrier and for waste conditioning in nuclear waste re-positories. Organic additives like poly(hydroxyl)carboxylates are commonly used for tuning the physico-chemical and mechanical properties of fresh concrete. In the worst-case scenario of wa-ter intrusion into the waste repository, the concrete may degrade, so that the soluble organic ad-ditives will be leached out and may form stable radionuclide (RN) complexes. Consequently, for a long-term risk assessment in nuclear waste repositories, the interactions of RNs with cement additives and CSH phases (main phase of cement) must be known. Americium(III) is one of the RN that will determine the radiotoxicity of a waste repository for a long time. As a model com-pound for cement additives malic acid (α-hydroxydicarboxylic acid) was chosen...

Concrete widely serves as an engineering barrier and for waste conditioning in nuclear waste re-positories. Organic additives like poly(hydroxyl)carboxylates are commonly used for tuning the physico-chemical and mechanical properties of fresh concrete. In the worst-case scenario of wa-ter intrusion into the waste repository, the concrete may degrade, so that the soluble organic ad-ditives will be leached out and may form stable radionuclide (RN) complexes. Consequently, for a long-term risk assessment in nuclear waste repositories, the interactions of RNs with cement additives and CSH phases (main phase of cement) must be known. Americium(III) is one of the RN that will determine the radiotoxicity of a waste repository for a long time. As a model com-pound for cement additives malic acid (α-hydroxydicarboxylic acid) was chosen...

The latest results in the Eu-B(OH)3-Organic System are presented: 1) New approach to determine the formation constant of a Eu borates 2) Formation of the solid Eu borate in NaCl medium 3) Quantitative synthesis of Eu borate and structure characterization

Boric acid (B(OH)3) and (poly)borates are of great interest regarding the mobilization of trivalent actinides in nuclear waste repositories, particularly in salt deposits. This work describes approaches to determine the stability constant in the Eu(III)-borate system. The stability constant between Eu(III) and borates is in the order of magnitude of 1...2, and with it the borate complexation is very weak. Furthermore, in presence of polyborates at pH 6 the formation of a solid Eu borate species is observed. The formation rate of the solid Eu borate species depends on the polyborate concentration and salt concentration/type (NaClO4/NaCl). Some structural information of the solid Eu borate were provided from IR spectroscopy, solid-state NMR (11B) and solid-state TRLFS.

Boric acid (B(OH)3) and (poly)borates are of great interest regarding the mobilization of trivalent actinides in nuclear waste repositories, particularly in salt deposits. This work describes the influence of boric acid on the Eu salicylate complexation due to the formation of a borate ester of salicylate, which could be the key to determine the stability constants of Eu-borate complexes. Furthermore, at pH 6 the formation of a solid Eu borate species in presence of polyborates is observed. The formation progress of the solid Eu borate species depends on the polyborate concentration and salt concentration. The solid formation could be an interesting possibility for the immobilization of trivalent actinides in a nuclear waste repository.

Concerning the safety and risk assessment for a nuclear waste repository the interaction between trivalent lanthanides and actinides and borates is interesting to study. Borates occur in salt deposits (possible host rock for nuclear waste repositories) and can be release due to corrosion of vitrified waste block (borosilicate glass) and storage containers. The investigations concentrate on the reaction between Eu(III) and borates in aqueous solution. At pH 6 the formation of a Eu borate solid species in presence of polyborates is observed. The formation of the solid Eu borate species depends on the polyborate concentration and ionic strength.

Clay minerals which are components of potential host rock formations for nuclear waste repositories can contain small organic molecules like formate, citrate or lactate. Such small organic molecules can like the ubiquitous humic acids influence the migration behavior of radionuclides. Different substituted benzoic acids can mimic the main functionalities and are often used as model compounds for humic substances. The understanding of the complex behavior of radionuclides with such natural organic matter and the thermodynamic quantification of the interaction especially at elevated temperatures is of great importance to simulate and predict their migration behavior in the environment, particularly in the near field of nuclear waste disposals where higher temperatures are prevailing. We present the investigation of the complex behavior of Am(III) and Eu(III) with lactate and salicylate at ambient and elevated temperatures with time-resolved laser-induced fluorescence spectroscopy (TRLFS) and the resulting thermodynamic data (reaction enthalpy, reaction entropy). Whereas the complexation with lactate is for both cations nearly temperature independent, is the complexation with salicylate clearly an endothermic reaction.

Argillaceous rocks, like the Opalinus clay formation (OPA) in Switzerland are potential host rocks for nuclear waste repositories. The OPA can contain up to 1% dissolved organic matter. It consists of small organic molecules like formiate, citrate or lactate. Such small organic molecules can like the ubiquitous humic acid influence the migration behaviour of radionuclides. The understanding of the complex behaviour of radionuclides with such natural organic matter and the thermodynamic quantification of the interaction is of great importance to simulate and predict their migration behaviour in the environment. Additionally, it is crucial to study the complex behaviour of radionuclides at elevated temperatures, because especially in the near field of nuclear waste disposals higher temperatures are prevailing. We investigated the complex behaviour of Am(III) complexes with lactate and substituted benzoic acids like pyromellitic acid (1,2,4,5-benzenetetracarboxylic acid, BTC) which serve as model compounds for humic substances at ambient and elevated temperatures with time-resolved laser-induced fluorescence spectroscopy (TRLFS). TRLFS has been extensively used as a sensitive and selective technique to analyze actinide complexation with inorganic and organic ligands in trace metal concentrations. However, the application of TRLFS onto Am(III) complex systems was up to now limited because of the much lower luminescence intensity and much shorter lifetime in comparison to U(VI) or Cm(III). Using the emission of the 5D1-7F1 transition at around 690 nm, spectral data like luminescence lifetimes and maxima and complex stability constants were calculated. Temperature dependent stability constants were determined to estimate thermodynamic data (enthalpy, entropy). The Am(III) aquo ion shows at pH 4-5 a luminescence lifetime of 23 ns, corresponding to approximately 9 coordinating water molecules. Complexation with BTC shows no change of the emission maximum but an increase of the luminescence intensity and lifetime. The luminescence lifetime was prolonged to 27 ns, corresponding to 8 remaining water molecules in the first coordination shell. This indicates an exchange of 1 water molecule with 1 coordination site of the ligand, resulting in an Am-BTC 1:1 complex. In contrast, complexation with lactate causes additionally a red shift of the luminescence maximum of about 5 nm. The luminescence lifetime is prolonged up to 37 ns which corresponds to 5-6 remaining water molecules, indicating an exchange of about 3-4 water molecules with coordination sites of ligand molecules which implies the formation of 1:1, 1:2 and 1:3 complexes. The stability constants increase with rising temperature which is consistent with an endothermic complexation reaction. TRLFS investigations with the inactive lanthanide analogue Eu(III) and the same ligands resulted in similar complex behaviour of Am(III) and Eu(III). This fact permits performing further investigations concerning the complex behaviour of trivalent actinides at elevated temperatures exemplarily with Eu(III). Temperature-dependent isothermal titration calorimetry (ITC) shows with rising temperature a stepwise polymerization between Eu(III) and BTC. ATR FT-IR (attenuated total reflection Fourier transform infrared spectroscopy) in combination with DFT (density functional theory) calculations was used to determine main structural features of the monomer and the polymer. In principle, we found monodentate coordination of one carboxylate group of BTC to one Eu(III) with a small fraction of chelating coordination mode of two neighbouring carboxylate groups. The results suggest that the migration of actinides will be strongly influenced by organic matter. Small organic molecules can enhance the mobility with rising temperature due to higher complexation ability. In contrast, complex organic materials like humic substances are able to immobilize radionuclides under certain conditions due to the possibility of polymerization.

Presently, argillaceous rock formations are under investigation as potential host rocks for nuclear waste repositories. In addition to the diffusion the sorption of radionuclides on mineral phases is an important physicochemical process in a nuclear waste repository in the case of a water inleakage. Concerning the required long-term safety and risk assessment of the storage of high-level radioactive waste the understanding of these processes is essential. Opalinus Clay (OPA) is a complex composed argillaceous rock. This natural occurring clay rock is discussed as host rock formation for nuclear waste repositories. In a repository based on argillaceous rock an initial temperature of around 100°C is expected due to the radioactive decay and the release of geothermal energy. But although elevated temperatures are able to influence the sorption behaviour of radionuclides on mineral phases the temperature effect is still investigated insufficiently. The investigations concentrated on the sorption of Eu(III) on OPA under realistic OPA pore water conditions (pH 7.6, I = 0.4 mol•L-1) up to 50°C. In addition to the temperature dependent investigations the influence of organic matter (tartrate, citrate) on the Eu(III) sorption on OPA was studied up to 50°C. The Eu(III) sorption is characterized by a very strong sorption to the clay surface. A significant temperature dependency of the Eu(III) sorption was observed. In the presence of tartrate or citrate the Eu(III) sorption decreases with rising ligand concentration. A surface species, most likely a EuCO3 surface species, was detected using TRLFS. The formation of a surface species containing tartrate or citrate was not observed with TRLFS.

Mittels UV-vis Spektroskopie wurden die Stabilitätskonstanten von Am-Citratkomplexen bei verschiedenen temperaturen zwischen 20 und 60°C bestimmt. Durch den Einsatz einer Liquid Waveguide Capillary Cell (LWCC) konnte mit sehr kleinen Am-Konzentrationen gemessen werden.

The complexation of the trivalent Americium ion with salicylic acid was investigated using a Liquid Waveguide Capillary Cell (LWCC) for UV/vis spectroscopy, enabling measurements at very low metal concentrations.

The long-term safety analysis of nuclear waste disposals in clay formations requires detailed knowledge of the interaction of actinides at relevant temperatures (up to 100 °C). It is well known that the migration behaviour of the actinides is strongly influenced by natural organic matter (NOM) from the clay. However, the current thermodynamic database is lacking fundamental data about the temperature-dependent complexation of americium (and its analogue europium) with small organic acids, which are structural similar components of natural organic matter in the clay. We present our results for the complexation of both Am(III) and Eu(III) with 2-hydroxybenzoic acid (salicylic acid), 1,2,4,5-benzentetracarboxylic acid (pyromellitic acid) and 2,3-dihydroxbutanedioic acid (L-tartaric acid) in the temperature range from 20 to 50°C, at ionic strength of 0.1 mol/l NaClO4 and pH below 6. For the first time, temperature-dependent UV-Vis spectroscopic measurements with a Liquid Waveguide Capillary Cell were used for complexation investigations. Due to the long optical path length of the capillary cell (up to 2 m) very low americium and europium concentrations can be measured. Thus, the presented absorption measurements were carried out at Am(III) concentrations below 5e-7 mol/l and Eu(III) concentration below 5e-4 mol/l. For all investigated model ligands we observed a slight shift of the absorption maxima of Eu(III) (394 nm) and Am(III) (504 nm) spectra of 0.5 to 2 nm to higher wavelengths due to the complexation. We first validated the method with europium: at 25°C the determined constants for the 1:1 complexes of europium salicylate, europium pyromellitate and europium L tartrate with logß111=15.4+/-0.06, logß112 = 14.3 +/-0.2, logß111=7.9+/-0.3 respectively, are in good agreement with the literature values [1], [2]. For the americium salicylate system, both a 1:1 complex and a 1:2 complex were observed at pH 4. The stability constants of these complexes are logß111= 15.42+/-0.06 and logß122=30.98+/-0.05 and comparable to the reported ones for the analogous complexes with europium [1]. With increasing temperature, the stability constants for both complex systems increase, indicating an endothermic complexation reaction. The same behaviour is expected for the americium pyromellitate system, where just a 1:1 complex with log ß112=15.03+/-0.1 can be reported until now. The temperature dependence and the interaction of americium with L-tartrate is presently under investigation. The stability constants and thermodynamic parameters (enthalpy, entropy, Gibbs energy) of all above investigated systems are reported. [1] Aoyagi, N. et al. Radiochemica Acta, Vol. 92, 2004, 589-593 [2] R. Kulshrestha, S. Sengar, M. Singh, Indian J. of Chemistry 26A, 1987, 940-943

Thermodynamic data for reactions of trivalent Actinides in the host rock environment are required for analysis of long-term safety of nuclear waste disposals in clay. We analyzed the complexation behaviour of Eu(III) and Am(III) with benzoic acid derivatives, which structures are similar to the natural organic matter.

Humic acids have a great influence on the migration of actinides and heavy metals. To get a quantitative understanding of the humic acid / actinide interaction on a molecular level, we investigate the complexation behavior of trivalent lanthanides and actinides with different functionalized benzoic acids as model compounds for humic acids. Our primary objective is to determine the temperature dependence of the complexation behavior, because in radioactive waste repositories one can observe elevated temperatures and concerning this matter only few investigations are known. In this study, we present the reaction of Eu(III) with 2-hydroxybenzoate (salicylate), 2,5-dihydroxybenzoate and 1,2,4,5-benzenetetracarboxylate (pyromellitate), investigated with time-resolved laser-induced fluorescence spectroscopy (TRLFS) at different temperatures (10-50°C). The Eu pyromellitate complex system shows strong luminescence behavior. The intensity of the 5D0 7F2 transition band increases with increasing ligand concentration. With increasing temperature, the total emission intensity decreases slightly. At lower pH (around 3) a MHL complex species with a stability constant of logK = 3.92 (25°C) could be determined. The lifetime of about 125 µs indicates, according to the equation of Kimura et al. (n(H2O) = 1.07 x (1/t -0.62) [1]), the exclusion of 1 water molecule from the first shell, implying an inner sphere complex with monodentate coordination. At pH around 5, a ML complex species (logK = 4.74, 25°C) was identified. The lifetime of about 135 µs stands for the substitution of 2 water molecules, according to an inner sphere complex with bidentate coordination. The lifetimes remain constant over the determined temperature range, as well as the lifetime of the free Eu3+(aq) ion. With increasing temperature, the stability constants increase, indicating an endothermic complexation reaction. The thermodynamic parameters of the Eu pyromellitate complexes were calculated to be ΔH = 9.4 kJ mol-1, ΔG = 22.3 kJ mol-1, ΔS = 106 J mol-1 K-1 (MHL; 25 °C) and ΔH = 15.2 kJ mol-1, ΔG = 28.1 kJ mol-1, ΔS = 145 J mol-1 K-1 (ML; 25 °C); these values are in good agreement with the literature [2]. The Eu complexes with salicylate and 2,5-dihydroxybenzoate show no luminescence behavior; only static and dynamic quenching is observable. For both ligands, the complex stability constants for a 1 : 1 complex species each could be determined. With increasing temperature, the stability constant also increases in both cases, indicating again an endothermic complexation reaction. The stability constants and thermodynamic parameters of these complexes are reported and compared with those determined by UV-vis spectroscopy with a liquid waveguide capillary cell (LWCC). [1] T. Kimura, G.R. Choppin, Y. Kato, Z. Yoshida, Radiochim. Acta 72 (1996) 61-64. [2] G.R. Choppin, E.N. Rizkalla, T.A. El-Ansi, A. Dadgar, J. Coord. Chem. 31 (1994) 297-304.

The combination of UV-vis spectroscopy with a LWCC results in a higher sensitivity and allows measurements at low heavy metal concentrations. We demonstrate the utility of the LWCC for the investigation of complex formation between heavy elements and organic substances by showing the first results achieved with Eu and Am.

In preparation for thermochromatographic adsorption studies of Lr in metal columns at temperatures up to 2000 K we investigated the metal adsorption of Cm and Bk. Cm was chosen to model Lr as a trivalent metal and Bk as a trivalent actinide having a (divalent) fn+1s2 ground state configuration. 250Bk electroplated on tantalum and 248Bk/246Cm implanted in zirconium foils were used as actinide sources. To carry out an adsorption experiment the actinide sources were placed at the starting position of the thermochromatographic columns and hold for 30 min at 1850 K. Standard enthalpies of adsorption were calculated from the experimental results and compared with calculations using a semi-empirical method. Based on these results, the capability of the method for studying electronic and metallic state properties of the heaviest actinides up to Lr is discussed.

This paper reports on the new control program CORA for the ROMA detection device. It was developed as part of the HITGAS apparatus for the study of seaborgium (Z=106) as oxide hydroxide. CORA runs under Win9x and Win NT. It is object oriented, programmed with Borland C++ Builder. Its main features are high flexibility for various experiment modes, hardware independence to a large extent, and an easy-to-understand user interface.

Seaborgium (element 106) was studied in comparison with tungsten in the O2-H2O(g)/SiO2(s)-system using high-temperature on-line isothermal gas chromatography. The 21-s nuclide 266Sg was produced in the 248Cm + 22Ne reaction at a beam energy of 119 MeV. The reaction products were continuously transported by a He(MoO3)-jet to the chromatography apparatus HITGAS. Group 6 element oxide hy-droxide molecules volatile at temperatures above 1000 K were formed at 1325 K by adding humid oxygen as reactive gas. 266Sg was unambiguously detected after gas chromatographic separation by measuring 266Sg-262Rf mother-daughter a-sf correlations. The experimental results demonstrate the volatility of seaborgium in humid oxygen, presumably as seaborgium oxide hydroxide as typical for both uranium (VI) and the group 6 elements.

A new computer program has been developed for the control of the GSI Rotating Wheel Multi Detector Apparatus (ROMA) running under the Windows 95 and Windows NT 4.0 operating systems. It can be fitted to a lot of detection tasks in a highly flexible way. The ROMA apparatus [1] has been used successfully for a lot of chemical investiga-tions of transactinide elements. In preparation of our seaborgium experiment at GSI in sum-mer 1998 [2] we developed a new control program. This was necessary because the old control code was running on an ATARI computer. In case of a damage of this computer, there would not have been the possibility of a replacement, which could possibly cancel the experiment. The new program was designed to fulfill our special experimental requirements. A second feature is its support of the usual working conditions in a long running beam time. That means, persons without a deep understanding of a computer should be able to use this program without any difficulties, even if the programmer is not available. Thirdly, it should be highly flexible in order to adapt it to new experimental demands. Finally, the program should be to a great extent independent of the experiment hardware in order to be usable for similar apparatuses. The program is written entire-ly in the C++ language using the Borland C++ Builder 1.0 programming environment based on the object oriented Virtual Component Library. The program has to carry out the following tasks: · control of the ROMA wheel movements according to the actual experiment; · enabling and disabling the nuclear spectros-copy data acquisition; · sending information about the actual ROMA status to the data acquisition hardware; · processing requests of the acquisition hardware (e. g. switching in "daughter mode" [3]); · processing user input (e. g. experiment and wheel setup dialog boxes). The program is a Microsoft Windows applicatio ...

Zur physikochemischen Charakterisierung des Seaborgiums ist die Hochtemperatur-Gaschromatographie im O2-H2O(g)/SiO2(s)-System gut geeignet. In Thermochromatographieexperimenten mit trägerfreien, langlebigen Nukliden der Sg-Homologen Cr, Mo und W wurde nachgewiesen, daß der Transport von Spurenmengen dieser Elemente im Unterschied zum Transport makroskopischer Mengen einheitlich erfolgt. In trockenem Sauerstoff werden monomere Trioxide gebildet, die über einfache reversible Adsorption durch die Chromatographiesäule transportiert werden. Wegen der geringen Flüchtigkeit dieser Verbindungsklasse kommt eine Charakterisierung des Sg als Trioxid jedoch nicht in Betracht. In feuchtem Sauerstoff bilden alle drei Sg-Homologen Oxidhydroxide, die reaktionsgaschromatographisch transportiert werden, wobei im adsorbierten Zustand wiederum das Trioxid vorliegt: MO2(OH)2(g) « MO3(ads) + H2O(g) Für diese Reaktion wurden thermodynamische Zustandsfunktionen bestimmt, die es erlauben, das Verhalten der Sg-Homologen unter veränderten experimentellen Bedingungen vorauszusagen und Sg-Experimente zu interpretieren. Modellexperimente im Hinblick auf die physikochemische Charakterisierung des Sg wurden unter Nutzung kurzlebiger, trägerfreier Mo- und W-Isotope mittels isothermer on-line Hochtemperatur-Gaschromatographie durchgeführt. Durch Optimierung der experimentellen Bedingungen und verschiedene methodische Neuentwicklungen gelang es, die Gesamtretentionszeit für W von » 90 s auf » 10 s zu senken. Für 166W mit einer Halbwertszeit von 18,8 s, die etwa der des 266Sg (t1/2 = 21 s) entspricht, wurde eine Maximalausbeute von 53 % erhalten. Erste Sg-Experimente im O2-H2O(g)/SiO2(s)-System sind für Juni/Juli 1998 geplant. Ergebnisse dieser Experimente sollen vorgestellt und diskutiert werden.