Oxidation potentials, Gibbs energies, enthalpies and entropies of actinide ions in aqueous solutions

International Nuclear Information System (INIS)

1977-01-01

The values of the Gibbs energy, enthalpy, and entropy of different actinide ions, thermodynamic characteristics of the processes of hydration of these ions, and the presently known ionization potentials of actinides are given. The enthalpy and entropy components of the oxidation potentials of actinide elements are considered. The curves of the dependence of the Gibbs energy of ion formation on the atomic number of the element and the Frost diagrams are analyzed. The diagram proposed by Frost represents the graphical dependence of the Gibbs energy of hydrated ions on the degree of oxidation of the element. Using the Frost diagram it is easy to establish whether a given ion is stable to disproportioning

f-state luminescence of lanthanide and actinide ions in solution

International Nuclear Information System (INIS)

Beitz, J.V.

1993-01-01

Detailed studies of the luminescence of aquated Am 3+ are presented in the context of prior lanthanide and actinide ion work. The luminescing state of aquated Am 3+ is confirmed to be 5 D l based on observed emission and excitation spectra. The luminescence lifetime of Am 3+ in H 2 O solution is (22 ± 3) ns and (155 ± 4) ns in D 2 O solution at 295 K. Judd-Ofelt transition intensity theory qualitatively describes the observed Am 3+ relative integrated fluorescence intensities. Recent luminescence studies on complexed trivalent f-element ions in solution are reviewed as to the similarities and differences between lanthanide ion 4f state and actinide ion 5f state properties

Sequestering agents for the removal of actinides from waste streams

Energy Technology Data Exchange (ETDEWEB)

Raymond, K.N.; White, D.J.; Xu, Jide; Mohs, T.R. [Univ. of California, Berkeley, CA (United States)

1997-10-01

The goal of this project is to take a biomimetic approach toward developing new separation technologies for the removal of radioactive elements from contaminated DOE sites. To achieve this objective, the authors are investigating the fundamental chemistry of naturally occurring, highly specific metal ion sequestering agents and developing them into liquid/liquid and solid supported actinide extraction agents. Nature produces sideophores (e.g., Enterobactin and Desferrioxamine B) to selectivity sequester Lewis acidic metal ions, in particular Fe(III), from its surroundings. These chelating agents typically use multiple catechols or hydroxamic acids to form polydentate ligands that chelate the metal ion forming very stable complexes. The authors are investigating and developing analogous molecules into selective chelators targeting actinide(IV) ions, which display similar properties to Fe(III). By taking advantage of differences in charge, preferred coordination number, and pH stability range, the transition from nature to actinide sequestering agents has been applied to the development of new and highly selective actinide extraction technologies. Additionally, the authors have shown that these chelating ligands are versatile ligands for chelating U(VI). In particular, they have been studying their coordination chemistry and fundamental interactions with the uranyl ion [UO{sub 2}]{sup 2+}, the dominant form of uranium found in aqueous media. With an understanding of this chemistry, and results obtained from in vivo uranium sequestration studies, it should be possible to apply these actinide(IV) extraction technologies to the development of new extraction agents for the removal of uranium from waste streams.

Advanced Extraction Methods for Actinide/Lanthanide Separations

International Nuclear Information System (INIS)

Scott, M.J.

2005-01-01

The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

Advanced Extraction Methods for Actinide/Lanthanide Separations

Energy Technology Data Exchange (ETDEWEB)

Scott, M.J.

2005-12-01

The separation of An(III) ions from chemically similar Ln(III) ions is perhaps one of the most difficult problems encountered during the processing of nuclear waste. In the 3+ oxidation states, the metal ions have an identical charge and roughly the same ionic radius. They differ strictly in the relative energies of their f- and d-orbitals, and to separate these metal ions, ligands will need to be developed that take advantage of this small but important distinction. The extraction of uranium and plutonium from nitric acid solution can be performed quantitatively by the extraction with the TBP (tributyl phosphate). Commercially, this process has found wide use in the PUREX (plutonium uranium extraction) reprocessing method. The TRUEX (transuranium extraction) process is further used to coextract the trivalent lanthanides and actinides ions from HLLW generated during PUREX extraction. This method uses CMPO [(N, N-diisobutylcarbamoylmethyl) octylphenylphosphineoxide] intermixed with TBP as a synergistic agent. However, the final separation of trivalent actinides from trivalent lanthanides still remains a challenging task. In TRUEX nitric acid solution, the Am(III) ion is coordinated by three CMPO molecules and three nitrate anions. Taking inspiration from this data and previous work with calix[4]arene systems, researchers on this project have developed a C3-symmetric tris-CMPO ligand system using a triphenoxymethane platform as a base. The triphenoxymethane ligand systems have many advantages for the preparation of complex ligand systems. The compounds are very easy to prepare. The steric and solubility properties can be tuned through an extreme range by the inclusion of different alkoxy and alkyl groups such as methyoxy, ethoxy, t-butoxy, methyl, octyl, t-pentyl, or even t-pentyl at the ortho- and para-positions of the aryl rings. The triphenoxymethane ligand system shows promise as an improved extractant for both tetravalent and trivalent actinide recoveries form

Selective extraction of americium(III) over europium(III) ions with pyridylpyrazole ligands. Structure-property relationships

Energy Technology Data Exchange (ETDEWEB)

Su, Dongping; Liu, Ying; Li, Shimeng; Ding, Songdong; Jin, Yongdong; Wang, Zhipeng; Hu, Xiaoyang; Zhang, Lirong [Department of chemistry, Sichuan University, Chengdu (China)

2017-01-18

To clarify the structure-property relationships of pyridylpyrazole ligands and provide guidance for the design of new and more efficient ligands for the selective extraction of actinides over lanthanides, a series of alkyl-substituted pyridylpyrazole ligands with different branched chains at different positions of the pyrazole ring were synthesized. Extraction experiments showed that the pyridylpyrazole ligands exhibited good selective extraction abilities for Am{sup III} ions, and the steric effects of the branched chain had a significant impact on the distribution ratios of Am{sup III} and Eu{sup III} ions as well as the separation factor. Moreover, both slope analyses and UV/Vis spectrometry titrations indicated the formation of a 1:1 complex of 2-(1-octyl-1H-pyrazol-3-yl)pyridine (C8-PypzH) with Eu{sup III} ions. The stability constant (log K) for this complex obtained from the UV/Vis titration was 4.45 ± 0.04. Single crystals of the complexes of 3-(2-pyridyl)pyrazole (PypzH) with Eu(NO{sub 3}){sub 3} and Sm(NO{sub 3}){sub 3} were obtained; PypzH acts as a bidentate ligand in the crystal structures, and the N atom with a bound H atom did not participate in the coordination. In general, this study revealed some interesting findings on the effects of the alkyl-chain structure and the special complexation between pyridylpyrazole ligands and Ln{sup III} ions. (copyright 2017 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants

International Nuclear Information System (INIS)

Toulemonde, V.; CEA Centre d'Etudes de la Vallee du Rhone, 30 -Marcoule

1995-01-01

The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author)

Kinetic of liquid-liquid extraction for uranyl nitrate and actinides (III) and lanthanides (III) nitrates by amide extractants; Cinetique d`extraction liquide-liquide du nitrate d`uranyle et des nitrates d`actinides (III) et de lanthanides (III) par des extractants a fonction amide

Energy Technology Data Exchange (ETDEWEB)

Toulemonde, V [CEA Centre d` Etudes Nucleaires de Saclay, 91 -Gif-sur-Yvette (France); [CEA Centre d` Etudes de la Vallee du Rhone, 30 -Marcoule (France). Dept. d` Exploitation du Retraitement et de Demantelement

1995-12-20

The kinetics of liquid-liquid extraction by amide extractants have been investigated for uranyl nitrate (monoamide extractants), actinides (III) and lanthanides (III) nitrates (diamide extractants). The transfer of the metallic species from the aqueous phase to the organic phase was studied using two experimental devices: ARMOLLEX (Argonne Modified Lewis cell for Liquid Liquid Extraction) and RSC (Rotating Stabilized Cell). The main conclusions are: for the extraction of uranyl nitrate by DEHDMBA monoamide, the rate-controlling step is the complexation of the species at the interface of the two liquids. Thus, an absorption-desorption (according to Langmuir theory) reaction mechanism was proposed; for the extraction of actinides (III) and lanthanides (III) nitrates in nitric acid media by DMDBTDMA diamide, the kinetic is also limited by interfacial reactions. The behavior of Americium and Europium is very similar as fare as their reaction kinetics are concerned. (author). 89 refs.

A novel dipicolinamide-dicarbollide synergistic solvent system for actinide extraction

Energy Technology Data Exchange (ETDEWEB)

Patil, Ajay Bhagwan [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Pune Univ. (India). Garware Research Centre; Pathak, Priyanath; Mohapatra, Prasanta Kumar [Bhabha Atomic Research Centre, Mumbai (India). Radiochemistry Div.; Shinde, Vaishali Sanjay [Pune Univ. (India). Garware Research Centre; Alyapyshev, M.Yu.; Babain, Vasiliy A. [Federal Agency for Atomic Energy, St. Petersburg (Russian Federation). V.G. Khlopin Radium Institute

2014-09-01

Solvent extraction studies of several actinide ions such as Am(III), U(VI), Np(IV), Np(VI), Pu(IV) were carried out from nitric acid medium using a synergistic mixture of N,N'-diethyl-N,N'-di(para)fluorophenyl-2,6-dipicolinamide, (DEtD(p)FPhDPA, DPA), and hydrogen dicarbollylcobaltate (H{sup +}CCD{sup -}) dissolved in phenyltrifluoromethylsulphone (PTMS). The effects of different parameters such as aqueous phase acidity (0.01-3 M HNO{sub 3}), oxidation states of metal ions, ligand concentration, nature of diluent and temperature on the extraction behavior of metal ions were studied. The extracted Am(III) species was determined as H{sup +}[Am(DPA){sub 2}(CCD){sub 4}]{sup -} With increasing aqueous phase acidities, the extractability of both Am(III) and Eu(III) was found to decrease. The synergistic mixture showed better extraction in mM concentrations as compared to previously studied dipicolinamides. The thermodynamic studies were performed to calculate heat of extraction reaction and the extraction constants. The proposed synergistic mixture showed good extraction for all the metal ions, though lanthanide actinide separation results are not encouraging. (orig.)

Development of ion beam sputtering techniques for actinide target preparation

Science.gov (United States)

Aaron, W. S.; Zevenbergen, L. A.; Adair, H. L.

1985-06-01

Ion beam sputtering is a routine method for the preparation of thin films used as targets because it allows the use of a minimum quantity of starting material, and losses are much lower than most other vacuum deposition techniques. Work is underway in the Isotope Research Materials Laboratory (IRML) at ORNL to develop the techniques that will make the preparation of actinide targets up to 100 μg/cm 2 by ion beam sputtering a routinely available service from IRML. The preparation of the actinide material in a form suitable for sputtering is a key to this technique, as is designing a sputtering system that allows the flexibility required for custom-ordered target production. At present, development work is being conducted on low-activity actinides in a bench-top system. The system will then be installed in a hood or glove box approved for radioactive materials handling where processing of radium, actinium, and plutonium isotopes among others will be performed.

Thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments

Energy Technology Data Exchange (ETDEWEB)

Rai, Dhanpat; Rao, Linfeng; Weger, H.T.; Felmy, A.R. [Pacific Northwest National Laboratory, WA (United States); Choppin, G.R. [Florida State University, Florida (United States); Yui, Mikazu [Japan Nuclear Cycle Development Inst., Tokai Works, Tokai, Ibaraki (Japan)

1999-01-01

This report provides thermodynamic data for predicting concentrations of Pu(III), Am(III), and Cm(III) in geologic environments, and contributes to an integration of the JNC chemical thermodynamic database, JNC-TDB (previously PNC-TDB), for the performance analysis of geological isolation system for high-level radioactive wastes. Thermodynamic data for the formation of complexes or compounds with hydroxide, chloride, fluoride, carbonate, nitrate, sulfate and phosphate are discussed in this report. Where data for specific actinide(III) species are lacking, the data were selected based on chemical analogy to other trivalent actinides. In this study, the Pitzer ion-interaction model is mainly used to extrapolate thermodynamic constants to zero ionic strength at 25degC. (author)

Angular overlap model in actinides

International Nuclear Information System (INIS)

Gajek, Z.; Mulak, J.

1991-01-01

Quantitative foundations of the Angular Overlap Model in actinides based on ab initio calculations of the crystal field effect in the uranium (III) (IV) and (V) ions in various crystals are presented. The calculations justify some common simplifications of the model and fix up the relations between the AOM parameters. Traps and limitations of the AOM phenomenology are discussed

Angular overlap model in actinides

Energy Technology Data Exchange (ETDEWEB)

Gajek, Z.; Mulak, J. (Polska Akademia Nauk, Wroclaw (PL). Inst. Niskich Temperatur i Badan Strukturalnych)

1991-01-01

Quantitative foundations of the Angular Overlap Model in actinides based on ab initio calculations of the crystal field effect in the uranium (III) (IV) and (V) ions in various crystals are presented. The calculations justify some common simplifications of the model and fix up the relations between the AOM parameters. Traps and limitations of the AOM phenomenology are discussed.

On-line separation of Pu(III) and Am(III) using extraction and ion chromatography

International Nuclear Information System (INIS)

Jernstroem, J.; Lehto, J.; Betti, M.

2007-01-01

An on-line method developed for separating plutonium and americium was developed. The method is based on the use of HPLC pump with three analytical chromatographic columns. Plutonium is reduced throughout the procedure to trivalent oxidation state, and is recovered in the various separation steps together with americium. Light lanthanides and trivalent actinides are separated with TEVA resin in thiocyanate/formic acid media. Trivalent plutonium and americium are pre-concentrated in a TCC-II cation-exchange column, after which the separation is performed in CS5A ion chromatography column by using two different eluents. Pu(III) is eluted with a dipicolinic acid eluent, and Am(III) with oxalic acid eluent. Radiochemical and chemical purity of the eluted plutonium and americium fractions were ensured with alpha-spectrometry. (author)

Rapid ion-exchange separations of actinides

International Nuclear Information System (INIS)

Usuda, Shigekazu

1988-01-01

For the purpose of studying short-lived actinide nuclides, three methods for rapid ion exchange separation of actinide elements with mineral acid-alcohol mixed media were developed: anion exchange with nitric acid-methyl alcohol mixed media to separate the transplutonium and rare earth elements from target material, U or Pu and Al catcher foils; anion exchange with hydrochloric acid-methyl alcohol media to separate Am+Cm, Bk and Cf+Fm from the target, catcher foils and major fission products; and cation exchange with hydrochloric acid-methyl alcohol media and with concentrated hydrochloric acid to separate the transplutonium elements as a group from the rare earths after eliminating the large amounts of U, Al, Cu, Fe etc. The methods enable one to perform rapid and effective separation at elevated temperature (90 deg C) and immediate source preparation for alpha-ray spectrometry. (author) 47 refs.; 10 figs

Actinide speciation in the environment

International Nuclear Information System (INIS)

Choppin, G.R.

2007-01-01

Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides are introduced into the aquatic system. Chemical speciation, oxidation state, redox reactions, and sorption characteristics are necessary in predicting solubility of the different actinides, their migration behaviors and their potential effects on marine biota. The most significant of these variables is the oxidation state of the metal ion as the simultaneous presence of more than one oxidation state for some actinides in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is much more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK sp ≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO 2 2+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO 3 ) is the limiting species for the solubility of Am(III) in sea water. Thorium(IV) is present as Th(OH) 4 , in colloidal form. The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in natural waters which must be considered in assessing the environmental behavior of actinides. Much is understood about sorption of actinides on surfaces, the mode of migration of actinides in such waters and the potential effects of these radioactive species on marine biota, but much more understanding of the behavior of the actinides in the environment is

Complexation of f elements by tripodal ligands containing aromatic nitrogens. Application to the selective extraction of actinides(III)

International Nuclear Information System (INIS)

Wietzke, Raphael

1999-01-01

This work initiates a research project, whose aim is the actinides(lll)/lanthanides(III) separation by liquid-liquid extraction. We were interested in the study of the coordination chemistry of lanthanides(III) and uranium(III) (uranium(III) as model for the actinides(III)), with the aim to show differences between the two families and to better understand the coordination properties involved in the extraction process. We studied the lanthanide(III) and uranium(III) complexation with tripodal ligands containing aromatic nitrogens. Several tripodal ligands were synthesized varying the type and the number of the donor atoms. The lanthanide(III) complexes have been characterized in the solid state and in solution (by several techniques: "1H NMR, ESMS, luminescence, UV spectrophotometry, conductometry). Differences in the coordination were found depending on the nature of the donor atoms. The new ligands, tris(2-pyrazinylmethyl)amine (tpza) et tris(N,N-diethyl-2-carbamoyl-6- pyridylmethyl)amine (tpaa), have shown a selectivity for the actinides(III) with promising results in liquid-liquid extraction. The comparison between the lanthanum(III) and uranium(III) complexes with the ligand tpza showed differences in the bonding nature, which could be attributed to a covalent contribution to the metal-ligand bond. (author) [fr

Extraction of tetravalent and hexavalent actinide ions by tetraheptylammonium nitrate

International Nuclear Information System (INIS)

Swarup, Rajendra; Patil, S.K.

1977-01-01

Extraction of Th(IV), Np(IV), Pu(IV), U(VI), Np(VI), and Pu(VI) by tetraheptylammonium nitrate in Solvesso-100 has been studied from nitric acid medium. Attempts were made to identify the complex species in the organic phase by studying the dependence of the distribution coefficient of the actinide on amine concentration and taking the absorption spectra of the organic phase containing actinide ions. A compound tetraheptylammonium trinitratodioxouranate (VI) has been isolated and characterised. (author)

A data base for thermodynamic modeling of +III actinide solubility in concentrated Na-Cl-SO4-CO3-PO4 electrolytes

International Nuclear Information System (INIS)

Novak, C.F.; Crafts, C.C.; Dhooge, N.J.

1995-01-01

The literature contains thermodynamic parameters for describing the chemical behavior of the following: Am(III) in dilute NaHCO 3 media; Nd(III) in dilute to concentrated Na 2 CO 3 and NaHCO 3 media; Pu(III) in dilute to concentrated NaCl media; Nd(III)/Am(III) in dilute to concentrated Na 2 SO 4 media; and Am(III) in NaH 2 PO 4 media. We have combined this information into a thermodynamic data base for the general +III actinide, An(III), using the analogy for chemical behavior of f-elements in the same oxidation state. This internally consistent data base is based on equilibrium thermodynamics and the specific ion interaction activity coefficient formalism of Pitzer. This data base forms the basis for the prediction of potential Am(III) and Pu(III) dissolved concentrations in the concentrated natural brines associated with the Waste Isolation Pilot Plant (WIPP) in Southeastern New Mexico, USA

Extraction characteristics of trivalent lanthanides and actinides in mixtures of dinonylnaphthalenesulfonic acid and carboxylic acids

International Nuclear Information System (INIS)

West, M.H.

1983-03-01

Dinonylnaphthalenesulfonic acid (HDNNS) has been shown to be an effective liquid cation exchanger for the extraction of metal ions. This extractant has proven to be successful in the extraction of trivalent lanthanides and actinides in the pH range of 2.0 to 3.0, although it shows little selectivity for individual ions because of its strong acid character. In an effort to improve the selectivity of HDNNS between trivalent lanthanides and actinides, carboxylic acids were added to the organic phase and the effects on the extraction characteristics of HDNNS were investigated. Three carboxylic acids - nonanoic, cyclohexanecarboxylic, and cyclohexanebutyric - were studied with the following metals: Am(III), Cm(III), Ce(III), Eu(III), and Tm(III). The distributions of the metal ions were studied holding the HDNNS concentration constant while varying the carboxylic acid concentrations over a range of 1.0 x 10 -5 M to 1.0 M. Results indicated that the greatest enhancement of the extraction occurred at a carboxylic acid concentration of 1.0 x 10 -2 M with negative effects occurring at 0.5 M and 1.0 M. The effects on the extraction of the trivalent lanthanides and actinides were interpreted in terms of the structural differences of the carboxylic acids, the effect of the carboxylic acids on the HDNNS extraction mechanism, and the ionic properties of the metals studied

Speciation of Am(III)/Eu(III) sorbed on γ-alumina. Effect of metal ion concentration

International Nuclear Information System (INIS)

Kumar, S.; Tomar, B.S.; Godbole, S.V.

2013-01-01

The present paper describes the speciation of Am(III)/Eu(III) sorbed on γ-alumina, and its evolution with changing metal ion concentration, studied using batch sorption experiment, time resolved fluorescence spectroscopy (TRFS), extended X-ray absorption fine structure (EXAFS) and surface Complexation modeling (SCM). Though numerous studies exist in the literature on the speciation of trivalent actinides and lanthanides on alumina surface, the mechanism of sorption at high metal ion concentrations is not yet fully understood. Batch sorption experiments of Am(III) on γ-alumina under varying condition of pH (3-10), ionic strength (0.005-0.1 M NaClO 4 ) and metal ion concentration (10 -7 -10 -4 M) were performed. Higher metal ion concentration was achieved by the addition of Eu(III) considering it as an analogue of Am(III). Time resolved fluorescence spectroscopy (TRFS) study of Eu(III) sorbed on γ-alumina at the metal ion concentration of 5.0 x 10 -5 M was carried out over pH 4 to 7. TRFS showed the presence of two surface species, with distinctly different fluorescence decay life times. The shorter lifetime value and its changing pattern with pH indicate the surface species corresponding to this component to be monodentate species > AlOAm 2+ and its hydrolyzed forms. The sorbed Eu 3+ species corresponding to the longer lifetime value has 2-3 water molecules in its first coordination sphere and is multidentate in its binding on alumina surface. Extended X-ray absorption fine structure (EXAFS) measurement of Eu:γ-Al 2 O 3 sorption systems at pH 6.18 and 7.15 corroborate the existence of two surface complexes. Further it suggests the edge sharing bidentate binding of Eu on AlO 6 octahedra as the co-ordination mode of the higher lifetime component. Surface Complexation Modeling (SCM) of Am(III)/Eu(III) sorption onto γ-alumina at pH ≤7 has been carried out using these two surface species. 2-pK surface complexation modeling coupled with constant capacitance model

Chemical Interaction between U(VI) and Eu(III) ions on a Silica Surface

International Nuclear Information System (INIS)

Park, K. K.; Cha, W. S.; Cho, H. R.; Im, H. J.; Jung, E. C.

2010-01-01

Understanding the chemical behavior of actinide in groundwater flow is important for assessing the possibility of its migration with water flow in the radioactive waste disposal site. Precipitation/ dissolution in groundwater and adsorption/desorption onto a geological solid surface would determine its migration. The sorption in a geochemical system was expected to be a reaction on a naturally equilibrated surface. However, the construction of a waste disposal facility could disturb this equilibrium state, induce a new reaction environment and affect a nanoscopic surface reaction of actinide. Uranium is ubiquitous in the natural environment and a representative element in a nuclear fuel cycle and in a high level radioactive waste. In oxic environments, it is typically present as uranyl oxocation (UO 2 2+ ), which is easily adsorbed and thereby removed from a solution in the near neutral pH range. This adsorption would form a new surface condition to give an unexpected adsorption behavior for other actinide ions. Eu(III) frequently is used as a chemical analogue of Am(III) and Cm(III) in migration chemistry. The adsorption phenomena has been interpreted with the help of a SCM(surface complexation model). Some spectroscopic techniques such as EPR (Electron Paramagnetic Resonance), IR (InfraRed), EXAFS (Extended X-ray Absorption Fine Structure) and TRLFS (Time Resolved Laser Fluorescence Spectroscopy) have been used for the identification of a modeled adsorbing species. In the case of fluorescence elements, TRLFS has advantages over other techniques for its high sensitivity being proportional to laser source intensity and good selectivity depending on specific transition and lifetime. This technique can be applied to a species on a solid surface not absorbing light such as silica. U(VI) and Eu(III) have fluorescente properties reflecting their coordination structure. In this study, the interaction between U(VI) and Eu(III) on a silica surface was studied by a

Development and demonstration of a new SANEX Partitioning Process for selective actinide(III)/lanthanide(III) separation using a mixture of CyMe{sub 4}BTBP and TODGA

Energy Technology Data Exchange (ETDEWEB)

Modolo, G.; Wilden, A.; Daniels, H. [Forschungszentrum Juelich GmbH (Germany). Institute for Energy and Climate Research, IEK-6, Nuclear Waste Management and Reactor Safety; Geist, A.; Magnusson, D. [Karlsruher Institut fuer Technologie, Karlsruhe (Germany). Inst. fuer Nukleare Entsorgung; Malmbeck, R. [European Commission, JRC, Karlsruhe (Germany). Inst. for Transuranium Elements (ITU)

2013-05-01

Within the framework of the European collaborative project ACSEPT, a new SANEX partitioning process was developed at Forschungszentrum Juelich for the separation of the trivalent minor actinides americium, curium and californium from lanthanide fission products in spent nuclear fuels. The development is based on batch solvent extraction studies, single-centrifugal contactor tests and on flow-sheet design by computer code calculations. The used solvent is composed of 6,6{sup '}-bis(5,5,8,8-tetramethyl-5,6,7,8-tetrahydrobenzo-[1,2-4]trizazin-3-yl)-[2,2{sup '}]-bipyridine (CyMe{sub 4}BTBP) and N,N,N{sup '},N{sup '}-tetraoctyldiglycolamide (TODGA) dissolved in n-octanol. A spiked continuous counter-current test was carried out in miniature centrifugal contactors with the aid of a 20-stage flow-sheet consisting of 12 extraction, 4 scrubbing and 4 stripping stages. A product fraction containing more than 99.9% of the trivalent actinides Am(III), Cm(III) and Cf(III) was obtained. High product/feed decontamination factors >1000 were achieved for these actinides. The trivalent lanthanides were directed to the raffinate of the process with the actinide (III) product stream being contaminated with less than 0.5 mass-% in the initial lanthanides. (orig.)

New field of actinides solution chemistry; electrochemical study on actinide ion transfer at the interface of two immiscible electrolyte solutions

Energy Technology Data Exchange (ETDEWEB)

Kitatsuji, Yoshihiro; Yoshida, Zenko [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment; Kudo, Hiroshi [Tohoku Univ., Graduate School of Science, Sendai, Miyagi (Japan); Kihara, Sorin [Kyoto Inst. of Technolgy, Dept. of Chemistry, Kyoto (Japan)

2002-04-01

A novel electrochemical method on the basis of a controlled electrolysis has been developed for the study of the ion transfer at the interface of two immiscible electrolyte solutions (ITIES). The controlled-potential electrolysis for ITIES (CPEITIES) was applied to the transfer of actinide ions, and Gibbs energies for the transfer of UO{sub 2}{sup 2+} and Am{sup 3+} from aqueous solution (w) to nitrobenzene solution (nb) were determined to be 71.7 and 113 kJ mol{sup -1}, respectively. The ion transfer potentials for the facilitated transfer of UO{sub 2{sup +}} and Am{sup 3+} from w to nb in the presence of bis(diphenylphosphoryl)methane were determined, from which the stability constants of UO{sub 2}(BDPPM){sub 3}{sup 2+} and Am(BDPPM){sub 3}{sup 3+} complexes involved in the facilitated ion transfer reaction, were calculated to be 10{sup 23.9} and 10{sup 27.5}, respectively. On the basis of the results of CPEITIES, a feasibility of a new separation method, i.e., an electrolytic ion transfer separation, of actinide ions is evaluated. (author)

Actinide-Aluminate Speciation in Alkaline Radioactive Waste

International Nuclear Information System (INIS)

Clark, David L.; Fedosseev, Alexander M.

2001-01-01

Investigation of behavior of actinides in alkaline media containing AL(III) showed that no aluminate complexes of actinides in oxidation states (IIII-VIII) were formed in alkaline solutions. At alkaline precipitation IPH (10-14) of actinides in presence of AL(III) formation of aluminate compounds is not observed. However, in precipitates contained actinides (IIV)<(VI), and to a lesser degree actinides (III), some interference of components takes place that is reflected in change of solid phase properties in comparison with pure components or their mechanical mixture. The interference decreases with rise of precipitation PH and at PH 14 is exhibited very feebly. In the case of NP(VII) the individual compound with AL(III) is obtained, however it is not aluminate of neptunium(VII), but neptunate of aluminium(III) similar to neptunates of other metals obtained earlier

Actinide science. Fundamental and environmental aspects

International Nuclear Information System (INIS)

Choppin, Gregory R.

2005-01-01

Nuclear test explosions and reactor wastes have deposited an estimated 16x10 15 Bq of plutonium into the world's aquatic systems. However, plutonium concentration in open ocean waters is orders of magnitude less, indicating that most of the plutonium is quite insolvable in marine waters and has been incorporated into sediments. Actinide ions in waters often are not in a state of thermodynamic equilibrium and their solubility and migration behavior is related to the form in which the nuclides were introduced into the aquatic system. Actinide solubility depends on such factors as pH(hydrolysis), E H (oxidation state), reaction with complexants (e.g. carbonate, phosphate, humic acid, etc.) sorption to surfaces of minerals and/or colloids, etc., in the water. The most significant of these variables is the oxidation sate of the metal ion. The simultaneous presence of more than one oxidation state for some actinides (e.g. plutonium) in a solution complicates actinide environmental behavior. Both Np(V)O 2 + and Pu(V)O 2 + , the most significant soluble states in natural oxic waters are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation but can undergo reduction to the Pu(IV) oxidation state with its different elemental behavior. The solubility of NpO 2 + can be as high as 10 -4 M while that of PuO 2 + is more limited by reduction to the insoluble tetravalent species, Pu(OH) 4 , (pK SP - 56). The net solubility of hexavalent UO 2 2+ in sea water is also limited by hydrolysis; however, it has a relatively high concentration due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(CO) 3 (OH), is the limiting species for the solubility of Am(III) in sea water. Thorium is found exclusively as the tetravalent species and its solubility is limited by the formation of quite insoluble Th(OH) 4 . The chemistry of actinide ions in the environment is reviewed to show the spectrum of reactions that can occur in

Simulation of alpha decay of actinides in iron phosphate glasses by ion irradiation

Energy Technology Data Exchange (ETDEWEB)

Dube, Charu L., E-mail: dubecharu@gmail.com; Stennett, Martin C.; Gandy, Amy S.; Hyatt, Neil C.

2016-03-15

Highlights: • Alpha decay of actinides in iron phosphate glasses is simulated by employing ion irradiation technique. • FTIR and Raman spectroscopic measurements confirm modification of glass network. • The depolymerisation of glass network after irradiation is attributed to synergetic effect of nuclear and electronic losses. - Abstract: A surrogate approach of ion beam irradiation is employed to simulate alpha decay of actinides in iron phosphate nuclear waste glasses. Bismuth and helium ions of different energies have been selected for simulating glass matrix modification owing to radiolysis and ballistic damage due to recoil atoms. Structural modification and change in coordination number of network former were probed by employing Reflectance Fourier-Transform Infrared (FT-IR), and Raman spectroscopies as a consequence of ion irradiation. Depolymerisation is observed in glass sample irradiated at intermediate energy of 2 MeV. Helium blisters of micron size are seen in glass sample irradiated at low helium ion energy of 30 keV.

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

Energy Technology Data Exchange (ETDEWEB)

Francois, N [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

2000-07-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands; Vers une interpretation des mecanismes de la separation actinides(III)/lanthanides(III) par extraction liquide-liquide synergique impliquant des ligands polyazotes

Energy Technology Data Exchange (ETDEWEB)

Francois, N. [CEA/VALRHO - site de Marcoule, Dept. de Recherche en Retraitement et en Vitrification, (DRRV), 30 - Marcoule (France); Universite Henri Poincare, 54 - Vandoeuvre-les-Nancy (France)

2000-07-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

Selective extraction of trivalent actinides with hard-soft mixed donor ligands: role of intra-ligand synergism

International Nuclear Information System (INIS)

Ghanty, Tapan K.

2016-01-01

In recent years, considerable attention has been given to understand the coordination chemistry of trivalent lanthanide (Ln) and actinide (An) with various ligands because of its close link with the nuclear waste management processes. It is well known that lanthanide-actinide separation is a challenging and difficult task because of very similar chemical properties of these two series of ions, which are associated with similar ionic radii and coordination numbers. Recently, we have introduced a new concept, 'intra-ligand synergism', where hard donor atom, such as, oxygen preferentially binds to trivalent actinides (An(III)) as compared to the valence iso-electronic trivalent lanthanides (Ln(III)) in presence of another soft donor centre. In the present work, the conventional concept of selective complexation of actinides with soft donor ligands (either S or N donor) has been modified through exploiting this concept, and thereby the higher selectivity of 1,10-phenanthroline-2,9-dicarboxylamide (PDAM) based ligands, namely PDAM and its isobutyl and decyl derivatives towards Am(III) ion has been predicted theoretically through density functional calculations. Subsequently, several such amide derivatives have been synthesized to optimize the solubility of the ligands in organic phase. Finally, solvent extraction experiments have been carried out to validate the theoretical prediction on the selectivity of oxygen donor ligands towards Am(III) as compared to Eu(III), and a maximum separation factor of about 51 has been achieved experimentally using 2,9-bis(N-decylaminocarbonyl)-1,10-phenanthroline ligand. The separation factor is increased with the decrease in pH, which is very interesting since extraction of the Am 3+ ion is considered to be important under highly acidic conditions from the nuclear waste management point of view. (author)

Development of ion beam sputtering techniques for actinide target preparation

International Nuclear Information System (INIS)

Aaron, W.S.; Zevenbergen, L.A.; Adair, H.L.

1985-01-01

Ion beam sputtering is a routine method for the preparation of thin films used as targets because it allows the use of minimum quantity of starting material, and losses are much lower than most other vacuum deposition techniques. Work is underway in the Isotope Research Materials Laboratory (IRML) at ORNL to develop the techniques that will make the preparation of actinide targets up to 100 μg/cm 2 by ion beam sputtering a routinely available service from IRML. The preparation of the actinide material in a form suitable for sputtering is a key to this technique, as is designing a sputtering system that allows the flexibility required for custom-ordered target production. At present, development work is being conducted on low-activity in a bench-top system. The system will then be installed in a hood or glove box approved for radioactive materials handling where processing of radium, actinium, and plutonium isotopes among others will be performed. (orig.)

Complexation of trivalent actinide ions (Am3+, Cm3+) with humic acid: a comparison of different experimental methods

International Nuclear Information System (INIS)

Kim, J.I.; Rhee, D.S.; Wimmer, H.; Buckau, G.; Klenze, R.

1993-01-01

The complexation of trivalent metal ions with humic acid has been studied at pH 4 and 5 in 0.1 M NaClO 4 by three different experimental methods, i.e. UV spectroscopy, time resolved laser fluorescence spectroscopy (TRLFS) and ultrafiltration. The direct speciation of the metal ion and its humate complex in the reaction process has been made by UV spectroscopy for Am(III) in the micromolar concentration range and by TRLFS for Cm(III) in the nanomolar concentration range. The ultrafiltration is used with the lowest pore size of filter (ca. 1 nm) to separate the uncomplexed metal ion from its complexed species. The concentrations of both metal ion and humic acid are varied in such a manner that the effective functional groups of the humic acid becomes loaded with metal ions from 1% to nearly 100%. The loading capacity of the humic acid for the trivalent metal ion, determined separately at each pH, is introduced into the evaluation of complexation constants. The variation of the metal ion concentration from 6 x 10 -8 mol/l to 4 x 10 -5 mol/l does not show any effect on the complexation reaction. The three different methods give rise to constants being comparable with one another. The average value of the constants thus determined is log β = 6.24±0.28 for the trivalent actinide ions. (orig.)

Liquid-liquid extraction kinetics of uranyl nitrate and actinides (III)-lanthanides nitrates by extractants with amide function

International Nuclear Information System (INIS)

Toulemonde, V.

1995-01-01

Nowadays, the most important part of electric power is generated by fission energy. But spent fuels have then to be reprocessed. The production of these reprocessed materials separately and with a high purity level is done according to a liquid-liquid extraction process (Purex process) with the use of tributyl phosphate as solvent. Optimization studies concerning the extracting agent have been undertaken. This work gives the results obtained for the uranyl nitrate and the actinides (III)-lanthanides (III) nitrates extraction by extractants with amide function (monoamide for U(VI) and diamide for actinides (III) and lanthanides (III)). The extraction kinetics have been studied in the case of a metallic specie transfer from the aqueous phase towards the organic phase. The experiments show that the nitrates extraction kinetics is limited by the complexation chemical reaction of the species at the interface between the two liquids. An adsorption-desorption interfacial reactional mechanism (Langmuir theory) is proposed for the uranyl nitrate. (O.M.)

Actinide production in the reaction of heavy ions with curium-248

International Nuclear Information System (INIS)

Moody, K.J.

1983-07-01

Chemical experiments were performed to examine the usefulness of heavy ion transfer reactions in producing new, neutron-rich actinide nuclides. A general quasi-elastic to deep-inelastic mechanism is proposed, and the utility of this method as opposed to other methods (e.g. complete fusion) is discussed. The relative merits of various techniques of actinide target synthesis are discussed. A description is given of a target system designed to remove the large amounts of heat generated by the passage of a heavy ion beam through matter, thereby maximizing the beam intensity which can be safely used in an experiment. Also described is a general separation scheme for the actinide elements from protactinium (Z=91) to mendelevium (Z=101), and fast specific procedures for plutonium, americium and berkelium. The cross sections for the production of several nuclides from the bombardment of 248 Cm with 18 O, 86 Kr and 136 Xe projectiles at several energies near and below the Coulomb barrier were determined. The results are compared with yields from 48 Ca and 238 U bombardments of 248 Cm. Simple extrapolation of the product yields into unknown regions of charge and mass indicates that the use of heavy ion transfer reactions to produce new, neutron-rich above-target species is limited. The substantial production of neutron-rich below-target species, however, indicates that with very heavy ions like 136 Xe and 238 U the new species 248 Am, 249 Am and 247 Pu should be produced with large cross sections from a 248 Cm target. A preliminary, unsuccessful attempt to isolate 247 Pu is outlined. The failure is probably due to the half life of the decay, which is calculated to be less than 3 minutes. The absolute gamma ray intensities from 251 Bk decay, necessary for calculating the 251 Bk cross section, are also determined

Mechanisms for the reduction of actinide ions by Geobacter sulfurreducens

International Nuclear Information System (INIS)

Renshaw, J.C.; Livens, F.R.; May, I.; Lloyd, J.R.

2005-01-01

Full text of publication follows: Three of the most problematic radioactive contaminants are the actinide elements uranium, neptunium and plutonium. All three pose considerable long-term environmental risks. The most stable environmental oxidation states of uranium and neptunium are VI and V, respectively, as the di-oxo cations [UO 2 ] 2+ and [NpO 2 ] + ; both are highly soluble and so are relatively mobile and biologically available in the environment. In similar conditions, plutonium mainly exists as Pu(IV), which forms a highly insoluble hydrous oxide, although is also environmentally stable in the more soluble III, V and VI oxidation states. The bio-reduction of U(VI) by anaerobic subsurface microorganisms has been the focus of much recent interest. Both Fe(III)- and sulfate-reducing bacteria have been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 , with c-type cytochromes involved in electron transfer to the actinide. Such transformations offer a strategy for the bio-remediation of uranium contaminated groundwater and a potential mechanism for the bio-deposition of uranium ores. The mechanism of U(VI). reduction has important implications for the potential microbial reduction of transuranic elements with environmentally stable lower oxidation states. Reduction of mobile 237 Np(V) to Np(IV) and subsequent precipitation may be advantageous whilst remobilization of immobile Pu(IV) as more soluble Pu(III) species could have important environmental implications. Conversely, selective reduction might allow targeting of particular radionuclide species. The model anaerobic bacterium Geobacter sulfurreducens is typical of those found in contaminated subsurface environments and has been shown to reduce soluble [U VI O 2 ] 2+ to insoluble U IV O 2 . In the course of this study we use X-ray absorption spectroscopy (XAS) to show that G. sulfurreducens reduces U(VI) by a one-electron reduction, forming an unstable [UO 2 ] + species which subsequently

Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides; Separation par extraction liquide-liquide des actinides(III) des lanthanides(III) par de nouvelles molecules: les picolinamides

Energy Technology Data Exchange (ETDEWEB)

Cordier, P Y [CEA Marcoule, Departement de Recherche en Retraitement et en Vitrification, 30 - Bagnols-sur-Ceze (France); [Clermont-Ferrand-2 Univ., 63 - Aubiere (France)

1996-07-01

In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author) 105 refs.

X-ray study of chemical bonding in actinides(IV) and lanthanides(III) hexa-cyanoferrates

International Nuclear Information System (INIS)

Dumas, T.

2011-01-01

Bimetallic cyanide molecular solids derived from Prussian blue are well known to foster long-range magnetic ordering and show an intense inter-valence charge transfer band resulting from an exchange interaction through the cyanide-bridge. For those reasons the ferrocyanide and ferricyanide building blocks have been chosen to study electronic delocalization and covalent character in actinide bonding using an experimental and theoretical approach based on X-ray absorption spectroscopy. In 2001, the actinide (IV) and early lanthanides (III) hexacyanoferrate have been found by powder X-ray diffraction to be isostructural (hexagonal, P6 3 /m group). Here, extended X-ray Absorption Fine Structure (EXAFS) at the iron K-edge and actinide L 3 -edge have been undertaken to probe the local environment of both actinides and iron cations. In an effort to describe the cyano bridge, a double edge fitting procedure including both iron and actinide edges and based on multiple scattering approach has been developed. We have also investigated the electronic properties of these molecular solids. Low energy electronic transitions have been used iron L 2,3 edge, nitrogen and carbon K-edge and also actinides N 4,5 edge to directly probe the valence molecular orbitals of the complex. Using a phenomenological approach, a clear distinctive behaviour between actinides and lanthanides has been shown. Then a theoretical approach using quantum chemistry calculation has shown more specifically the effect of covalency in the actinide-ferrocyanide bond. More specifically, π interactions were underlined by both theoretical and experimental methods. Finally, in agreement with the ionic character of the lanthanide bonding no inter-valence charge transfer has been observed in the corresponding optical spectra of these compounds. On the contrary, optical spectra for actinides adducts (except for thorium) show an intense inter-valence charge transfer band like in the transition metal cases which is

Synthesis and structural characterisation of mixed An(IV)-An(III) actinide oxalates used as precursors for dedicated fuel or target

International Nuclear Information System (INIS)

Tamain, Christelle; Grandjean, Stephane; Arab Chapelet, Benedicte; Abraham, Francis

2010-01-01

Oxalic co-conversion process plays an important role by producing mixed-actinide compounds used as starting materials as they are particularly suitable precursors of actinide oxide solid solutions. In these oxalate compounds, a mixed crystallographic site which accommodates both elements in spite of their different oxidation states has been established. The charge compensation is ensured by monovalent cations present in the acidic solution. This communication reviews the various mixed-actinide oxalates obtained by crystallization from acidic solution. First, crystallographic structures determined by X-ray diffraction from single crystals are described. Then completing data obtained by powder X-ray diffraction are presented on various systems. The different supramolecular arrangements underline the complexity of An(IV)-An(III)/Ln(III) oxalate system and the need to pursue studies on single crystals. (authors)

Electro-spray Ionization Mass Spectrometry Investigation of BTBP - Lanthanide(III) and Actinide(III) Complexes

Energy Technology Data Exchange (ETDEWEB)

Retegan, T.; Ekberg, Ch. [Chalmers, Dept Chem and Biol Engn, SE-41296 Gothenburg, (Sweden); Berthon, L.; Zorz, N. [DEN DRCP SCPS LCSE, CEA Marcoule, Bagnols Sur Ceze, (France)

2009-07-01

In the framework of nuclear waste reprocessing, the separation processes of minor actinides from fission products are developed using liquid-liquid extraction. To gain an understanding of the mechanism involved in the extraction process, a complex formation of actinides and lanthanides with BTBPs (6, 6'-bis(5, 6-dialkyl-1, 2, 4-triazin-3-yl)-2, 2'-bipyridines) was characterized using the Electro-spray Ionization Mass Spectrometry (ESI-MS) technique. This study was carried out to compare the influence of diluents and side groups of the extractants on complex formation. Three different diluents, nitrobenzene, octanol and cyclohexanone, and two extractants, C5-BTBP and CyMe{sub 4}-BTBP, were selected for this experiment. It was found that the change of the diluent and of the substituent on the BTBP moiety does not modify the stoichiometry of the complexes which is L{sub 2}M(NO{sub 3}){sub 3}. It is proposed that one nitrate is directly coordinated to the metal ion, the two other anions probably remaining in the outer coordination sphere. The difference observed in extracting properties is probably due to the solvation of the complexes by the diluent. The noncovalent force that holds complexes together are likely to be largely governed by electrostatic interactions even if the hydrophobic exterior of the complexes plays an important role in the complexation/extraction mechanism. The study of the stability of the ions in the gas phase shows that the C5-BTBP ligand has a labile hydrogen atom, which is a fragility point of C5-BTBP. (authors)

Investigation of the separation of americium(III) and europium(III) by high-speed countercurrent chromatography

International Nuclear Information System (INIS)

Wu, J.F.; Jin, Y.R.; Xu, Q.C.; Wang, S.L.; Zhang, L.X.

2005-01-01

The long-lived actinides are the important elements in the radioactive waste ;disposal. Because the ions semi diameter and chemical properties of trivalent actinides(III) and trivalent lanthanides(III) are very similar, the separation between them is very difficult. Yang Yu-Sheng put forward the actinides(III) are softer acid than the lanthanides(III), so the actinides(III) are more easily extracted by the soft extractant contain sulfur or nitrogen than the lanthanides(III). Some research have been done on the separation between actinides(III) and lanthanides(III) using the extractants contain sulfur or nitrogen. The results show that satisfactory separation efficiency was gained. Countercurrent Chromatography (CCC) have many specific advantages, such as free from solid support, permit large sample volume and high flow rate, which is useful in the preconcentration of inorganic solute and inorganic preparation. Some studies were done on the separation of lanthanides or-other inorganic elements by HSCCC, the high-purity reagents prepared by HSCCC or CPC turned out to be successful. In present paper, the investigation of separation between Americium (III) and Euricium (III) by High-Speed Countercurrent Chromatography (HSCCC) were made. The extractant used in the work was prepared by ourselves, which is of the soft extractant contrain sulfur. The effects of separation condition on the separation efficiency of Am and Eu by HSCCC were investigated using dichlorophenyl dithiophosphinic acid in xylene as the stationary phase and 0.1 mol/L NaClO4 as mobile phase, respectively. The results show that mutual separation between Am and Eu can be accomplished. The separation factor increases with the increasing of the concentration of extractant and the pH value of the mobile phase, further more, minishing the flow rate of the mobile phase can also improves the separation efficiency between Am and Eu. The nearly base separation was gained when the flow rate is 0.35 ml/min, the

Extraction of lanthanides and actinides (III) by DI-2 ethyl dithiophosphoric acid and DI-2 ethyl hexyl monothiophosphoric acid. Structure of the complexes in the organic phase

International Nuclear Information System (INIS)

Pattee, D.; Musikas, C.; Faure, A.; Chachaty, C.

1986-09-01

To operate a trivalent actinide-lanthanide (III) group chemical separation from low pH nitric solutions we studied the extractive properties of the di-2 ethyl hexyl dithiophosphoric acid (HDEHDTP); this bidentate ligand which possesses a sulfur donor atom is a good extractant of soft acids. We so expect a better selectivity for the actinides (III) extraction. We also have investigated extractive properties of di-2 ethyl hexyl monothiophosphoric acid (HDEHTP) for trivalent actinides and lanthanides; HDEHDTP is a bidentate ligand with one oxygen donor atom and so is a better extractant for hard acids like actinides and lanthanides (III); but its selectivity is weak. The addition of TBP (tri-n butyl phosphate) to HDEHDTP deals to strong synergistic organic complexes with a great selectivity for Am(III). We explicited this phenomenon. When the metal is macroconcentrated the organic complexes aggregate and form inverted micelles

Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

Energy Technology Data Exchange (ETDEWEB)

Novak, C.F. [ed.

1995-08-01

This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media.

Actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP): FY94 results

International Nuclear Information System (INIS)

Novak, C.F.

1995-08-01

This document contains six reports on actinide chemistry research supporting the Waste Isolation Pilot Plant (WIPP). These reports, completed in FY94, are relevant to the estimation of the potential dissolved actinide concentrations in WIPP brines under repository breach scenarios. Estimates of potential dissolved actinide concentrations are necessary for WIPP performance assessment calculations. The specific topics covered within this document are: the complexation of oxalate with Th(IV) and U(VI); the stability of Pu(VI) in one WIPP-specific brine environment both with and without carbonate present; the solubility of Nd(III) in a WIPP Salado brine surrogate as a function of hydrogen ion concentration; the steady-state dissolved plutonium concentrations in a synthetic WIPP Culebra brine surrogate; the development of a model for Nd(III) solubility and speciation in dilute to concentrated sodium carbonate and sodium bicarbonate solutions; and the development of a model for Np(V) solubility and speciation in dilute to concentrated sodium Perchlorate, sodium carbonate, and sodium chloride media

X-ray absorption spectroscopic study of trivalent and tetravalent actinides in solution at varying pH values

Energy Technology Data Exchange (ETDEWEB)

Brendebach, B.; Banik, N.L.; Marquardt, C.M.; Rothe, J.; Denecke, M.A.; Geckeis, H. [Forschungszentrum Karlsruhe (Germany). Inst. fuer Nukleare Entsorgung

2009-07-01

We perform X-ray absorption spectroscopy (XAS) investigations to monitor the stabilization of redox sensitive trivalent and tetravalent actinide ions in solution at acidic conditions in a pH range from 0 to 3 after treatment with holding reductants, hydroxylamine hydrochloride (NH{sub 2}OHHCl) and Rongalite (sodium hydroxymethanesulfinate, CH{sub 3}NaO{sub 3}S). X-ray absorption near edge structure (XANES) measurements clearly demonstrate the stability of the actinide species for several hours under the given experimental conditions. Hence, structural parameters can be accurately derived by extended X-ray absorption fine structure (EXAFS) investigations. The coordination structure of oxygen atoms belonging to water ligands surrounding the actinide ions does not change with increasing pH value (approximately 11 O atoms at 2.42 A in the case of U(IV) at pH 1, 9 0 atoms at 2.52 A for Np(III) at pH 1.5, and 10 O atoms at 2.49 A for Pu(III) up to pH 3), indicating that hydrolysis reactions are suppressed under the given chemical conditions. (orig.)

Specific sequestering agents for iron and the actinides

Energy Technology Data Exchange (ETDEWEB)

Raymond, K.N.

1983-06-01

The transuranium actinide ions represent one unique environmental hazard associated with the waste of the nuclear power industry. A major component associated with that waste and a potential hazard is plutonium. The synthesis of metal-ion-specific complexing agents for ions such as Pu(IV) potentially represents a powerful new approach to many of the problems posed by waste treatment. This document is a progress report of a rational approach to the synthesis of such chelating agents based on the similarities of Pu(IV) and Fe(III), the structures of naturally-occurring complexing agents which are highly specific for Fe(III), and the incorporation of the same kinds of ligating groups present in the iron complexes to make octadentate complexes highly specific for plutonium. Both thermodynamic and animal test results indicate that a relatively high degree of success has already been achieved in this aim.

Towards an interpretation of the mechanism of the actinides(III)/lanthanides(III) separation by synergistic solvent extraction with nitrogen-containing polydendate ligands

International Nuclear Information System (INIS)

Francois, N.

2000-01-01

In the field of the separation of long-lived radionuclides from the wastes produced by nuclear fuel reprocessing, aromatic nitrogen-containing polydendate ligands are potential candidates for the selective extraction, alone or in synergistic mixture with acidic extractants, of trivalent actinides from trivalent lanthanides. The first part of this work deals with the complexation of trivalent f cations with various nitrogen-containing ligands (poly-pyridine analogues). Time-resolved laser-induced fluorimetry (TRLIF) and UV-visible spectrophotometry were used to determine the nature and evaluate the stability of each complex. Among the ligands studied, the least basic Me-Btp proved to be highly selective towards americium(III) in acidic solution. In the second part, two synergistic systems (nitrogen-containing polydendate ligand and lipophilic carboxylic acid) are studied and compared in regard to the extraction and separation of lanthanides(III) and actinides(III). TRLIF and gamma spectrometry allowed the nature of the extracted complexes and the optimal conditions of efficiency of both systems to be determined. Comparison between these different studies showed that the selectivity of complexation of trivalent f cations by a given nitrogen-containing polydendate ligand could not always be linked to the Am(III)Eu(III) selectivity reached in synergistic extraction. The latter depends on the 'balance' between the acid-basic properties on the one hand, and on the hard-soft characteristics on the other hand, of both components of synergistic system. (author)

DEVELOPMENT OF PROTOTYPE TITANATE ION EXCHANGE LOADED MEMBRANES FOR STRONTIUM, CESIUM AND ACTINIDE DECONTAMINATION FROM AQUEOUS MEDIA

Energy Technology Data Exchange (ETDEWEB)

Oji, L; Keisha Martin, K; David Hobbs, D

2008-05-30

We have successfully incorporated high surface area particles of titanate ion exchange materials (monosodium titanate and crystalline silicotitanate) with acceptable particle size distribution into porous and inert support membrane fibrils consisting of polytetrafluoroethylene (Teflon{reg_sign}), polyethylene and cellulose materials. The resulting membrane sheets, under laboratory conditions, were used to evaluate the removal of surrogate radioactive materials for cesium-137 and strontium-90 from high caustic nuclear waste simulants. These membrane supports met the nominal requirement for nonchemical interaction with the embedded ion exchange materials and were porous enough to allow sufficient liquid flow. Some of this 47-mm size stamped out prototype titanium impregnated ion exchange membrane discs was found to remove more than 96% of dissolved cesium-133 and strontium-88 from a caustic nuclear waste salt simulants. Since in traditional ion exchange based column technology monosodium titanate (MST) is known to have great affinity for the sorbing of other actinides like plutonium, neptunium and even uranium, we expect that the MST-based membranes developed here, although not directly evaluated for uptake of these three actinides because of costs associated with working with actinides which do not have 'true' experimental surrogates, would also show significant affinity for these actinides in aqueous media. It was also observed that crystalline silicotitanate impregnated polytetrafluoroethylene or polyethylene membranes became less selective and sorbed both cesium and strontium from the caustic aqueous salt simulants.

Complexation of the actinides (III, IV and V) with organic acids

International Nuclear Information System (INIS)

Leguay, S.

2012-01-01

A thorough knowledge of the chemical properties of actinides is now required in a wide variety of fields: extraction processes involved in spent fuel reprocessing, groundwater in the vicinity of radioactive waste packages, environmental and biological media in the case of accidental release of radionuclides. In this context, the present work has been focused on the complexation of Am(III), Cm(III), Cf(III), Pu(IV) and Pa(V) with organic ligands: DTPA, NTA and citric acid. The complexation of pentavalent protactinium with citric and nitrilotriacetic acids was studied using liquid-liquid extraction with the element at tracer scale (C Pa ≤ 10 -10 M). The order and the mean charge of each complex were determined from the analysis of the systematic variations of the distribution coefficient of Pa(V) as function of ligand and proton concentration. Then, the apparent formation constants related of the so-identified complexes were calculated. The complexation of trivalent actinides with DTPA was studied by fluorescence spectroscopy (TRLFS) and capillary electrophoresis (CE-ICP-MS). The coexistence of the mono-protonated and non-protonated complexes (AnHDTPA - and AnDTPA 2- ) in acidic media (1.5 ≤ pH ≤ 3.5) was shown unambiguously. Literature data have been reinterpreted by taking into account both complexes and a consistent set of formation constants of An(III)-DTPA has been obtained. The experimental study was completed by theoretical calculations (DFT) on Cm-DTPA system. The coordination geometry of Cm in CmDTPA 2- and CmHDTPA - including water molecules in the first coordination sphere has been determined as well as interatomic distances. Finally, a study on the complexation of Pu(IV) with DTPA was initiated in order to more closely mimic physiological conditions. A three-step approach was proposed to avoid plutonium hydrolysis: i/ complexation of Pu(IV) with (NTA) in order to protect Pu(IV) from hydrolysis (at low pH) ii/ increase of pH toward neutral conditions

Thermodynamic Properties of Actinides and Actinide Compounds

Science.gov (United States)

Konings, Rudy J. M.; Morss, Lester R.; Fuger, Jean

The necessity of obtaining accurate thermodynamic quantities for the actinide elements and their compounds was recognized at the outset of the Manhattan Project, when a dedicated team of scientists and engineers initiated the program to exploit nuclear energy for military purposes. Since the end of World War II, both fundamental and applied objectives have motivated a great deal of further study of actinide thermodynamics. This chapter brings together many research papers and critical reviews on this subject. It also seeks to assess, to systematize, and to predict important properties of the actinide elements, ions, and compounds, especially for species in which there is significant interest and for which there is an experimental basis for the prediction.

Separation by liquid-liquid extraction of actinides(III) from lanthanides(III) using new molecules: the picolinamides

International Nuclear Information System (INIS)

Cordier, P.Y.

1996-07-01

In the field of long-lived radionuclides separation from waste generated during spent fuel reprocessing, the picolinamides have been chosen as potential extractants for the selective extraction of actinides (III) from lanthanides (III). The first studies initiated on the most simple molecule of the picolinamide family, namely 2-pyridinecarboxamide, pointed out that in an aqueous media the complexation stability constant between this ligand and Am(III) is roughly 10 times higher than the ones corresponding to Ln(III). The synthesis of lipophilic derivatives of 2-pyridinecarboxamide leaded to extraction experiments. The extraction of metallic cation by lipophilic picolinamides, according to a solvatation mechanism, is strongly dependent on the nature of the amide function: a primary amide function (group I) leads to a good extraction; on the contrary, there is a decrease for secondary (group II) and tertiary (group III) amide functions. From a theoretical point of view, this work leads finally to the following conclusions: confirmation of the importance of the presence of soft donor atoms within the extractants (nitrogen in our case) for An(III)/Ln(III). Also, sensitivity of this soft donor atom regarding the protonation reaction; prevalence in our case of the affinity of the extractant for the metallic cation over the lipophilia of the extractant to ensure good distribution coefficients. The extraction and Am(III)/Ln(III) separation performances of the picolinamides from pertechnetic media leads to the design of a possible flowsheet for the reprocessing of high level liquid waste, with the new idea of an integrated technetium reflux. (author)

Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J.; Addleman, Raymond S.; Hay, Benjamin P.; Hubler, Timothy L.; Levitskaia, Tatiana G.; Sinkov, Sergey I.; Snow, Lanee A.; Warner, Marvin G.; Latesky, Stanley L.

2006-11-17

In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?= C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO

Selective Media for Actinide Collection and Pre-Concentration: Results of FY 2006 Studies

International Nuclear Information System (INIS)

Lumetta, Gregg J.; Addleman, Raymond S.; Hay, Benjamin P.; Hubler, Timothy L.; Levitskaia, Tatiana G.; Sinkov, Sergey I.; Snow, Lanee A.; Warner, Marvin G.; Latesky, Stanley L.

2006-01-01

In this work, we have investigated new materials for potential use in automated radiochemical separations. The work can be divided into three primary tasks: (1) synthesis of new ligands with high affinity for actinide ions, (2) evaluation of new materials for actinide ion affinity, and (3) computational design of advanced ligand architectures for highly selective binding of actinide ions. Ligand Synthesis Work was conducted on synthesizing Kl?ui ligand derivatives containing functionalized pendant groups on the cyclopentadienyl ring. The functionalized pendent groups would allow these ligands to be attached to organic and inorganic solid supports. This work focused on synthesizing the compound Na[Cp?Co(PO(OC2H5)2)3], where Cp?C5H4C(O)OCH3. Synthesizing this compound is feasible, but the method used in FY 2006 produced an impure material. A modified synthetic scheme has been developed and will be pursued in FY 2007. Work was also initiated on synthesizing bicyclic diamides functionalized for binding to polymeric resins or other surfaces. Researchers at the University of Oregon are collaborators in this work. To date, this effort has focused on synthesizing and characterizing a symmetrically substituted bicyclic diamide ligand with the ?COOH functionality. Again, this synthetic effort will continue into FY 2007. Separations Material Evaluation Work was conducted in FY 2006 to provide a more extensive set of data on the selectivity and affinity of extraction chromatography resins prepared by sorption of Kl?ui ligand onto an inert macroreticular polymeric support. Consistent with previous observations, it was found that these materials strongly bind tetravalent actinides. These materials also adsorb trivalent actinides at low nitric acid concentrations, but the affinity for the trivalent actinides decreases with increasing nitric acid concentration. These materials have relatively low affinity for U(VI), but they do sorb U(VI) to a greater extent than Am(III) at [HNO3

A literature review of actinide-carbonate mineral interactions

International Nuclear Information System (INIS)

Stout, D.L.

1993-10-01

Chemical retardation of actinides in groundwater systems is a potentially important mechanism for assessing the performance of the Waste Isolation Pilot Plant (WIPP), a facility intended to demonstrate safe disposal of transuranic waste. Rigorous estimation of chemical retardation during transport through the Culebra Dolomite, a water-bearing unit overlying the WIPP, requires a mechanistic understanding of chemical reactions between dissolved elements and mineral surfaces. This report represents a first step toward this goal by examining the literature for pertinent experimental studies of actinide-carbonate interactions. A summary of existing models is given, along with the types of experiments on which these models are based. Articles pertaining to research into actinide interactions with carbonate minerals are summarized. Select articles involving trace element-carbonate mineral interactions are also reviewed and may serve as templates for future research. A bibliography of related articles is included. Americium(III), and its nonradioactive analog neodymium(III), partition strongly from aqueous solutions into carbonate minerals. Recent thermodynamic, kinetic, and surface studies show that Nd is preferentially removed from solution, forming a Nd-Ca carbonate solid solution. Neptunium(V) is rapidly removed from solution by carbonates. Plutonium incorporation into carbonates is complicated by multiple oxidation states. Little research has been done on the radium(H) and thorium(IV) carbonate systems. Removal of uranyl ion from solution by calcite is limited to monolayer surface coverage

Research for actinides extractants from various wastes

International Nuclear Information System (INIS)

Musikas, C.; Cuillerdier, C.; Condamines, N.

1990-01-01

This paper is an overview of the actinides solvent extraction research undertaken in Fontenay-aux-Roses. Two kinds of extractants are investigated; those usable for the improvement of the nowadays nuclear fuels reprocessing and those necessary for advanced fuels cycles which include the minor actinides (Np, Am) recovery for a further elimination through nuclear reactions. In the first class the mono and diamides, alternative to the organophosphorus extractants, TBP and polyfunctional phosphonates, showed promising properties. The main results are discussed. For the future efficient extractants for trivalent actinides-lanthanides group separations are suitable. The point about the actinides (III) - lanthanides (III) group separation chemistry and the development of some of these extractants are given

Research on Actinides in Nuclear Fuel Cycles

International Nuclear Information System (INIS)

Song, Kyu Seok; Park, Yong Joon; Cho, Young Hwan

2010-04-01

The electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipment, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media

Research on Actinides in Nuclear Fuel Cycles

Energy Technology Data Exchange (ETDEWEB)

Song, Kyu Seok; Park, Yong Joon; Cho, Young Hwan

2010-04-15

The electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipment, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media

Actinide partitioning-transmutation program final report. III. Transmutation studies

International Nuclear Information System (INIS)

Wachter, J.W.; Croff, A.G.

1980-07-01

Transmutation of the long-lived nuclides contained in fuel cycle wastes has been suggested as a means of reducing the long-term toxicity of the wastes. A comprehensive program to evaluate the feasibility and incentives for recovering the actinides from wastes (partitioning) and transmuting them to short-lived or stable nuclides has been in progress for 3 years under the direction of Oak Ridge National Laboratory (ORNL). This report constitutes the final assessment of transmutation in support of this program. Included are (1) a summary of recent transmutation literature, (2) a generic evaluation of actinide transmutation in thermal, fast, and other transmutation devices, (3) a preliminary evaluation of 99 Tc and 129 I transmutation, and (4) a characterization of a pressurized-water-reactor fuel cycle with and without provisions for actinide recovery and transmutation for use in other parts of the ORNL program. The principal conclusion of the report is that actinide transmutation is feasible in both thermal and fast reactors, subject to demonstrating satisfactory fuel performance, with relatively little impact on the reactor. It would also appear that additional transmutation studies are unwarranted until a firm decision to proceed with actinide transmutation has been made by the responsible authorities

Solvent extraction of anionic chelate complexes of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) with 2-thenoyltrifluoroacetone as ion-pairs with tetrabutylammonium ions

International Nuclear Information System (INIS)

Noro, Junji; Sekine, Tatsuya.

1992-01-01

The solvent extraction of lanthanum(III), europium(III), lutetium(III), scandium(III), and indium(III) in 0.1 mol dm -3 sodium nitrate solutions with 2-thenoyltrifluoroacetone (Htta) in the absence and presence of tetrabutylammonium ions (tba + ) into carbon tetrachloride was measured. The extraction of lanthanum(III), europium(III), and lutetium(III) was greatly enhanced by the addition of tba + ; this could be explained in terms of the extraction of a ternary complex, M(tta) 4 - tba + . However, the extractions of scandium(III) and indium(III) were nearly the same when tba + was added. The data were treated on the basis of the formation equilibrium of the ternary complex from the neutral chelate, M(tta) 3 , with the extracted ion-pairs of the reagents, tta - tba + , in the organic phase. It was concluded that the degree of association of M(tta) 3 with the ion-pair, tta - tba + , is greater in the order La(tta) 3 ≅ Eu(tta) 3 > Lu(tta) 3 , or that the stability of the ternary complex in the organic phase is higher in the order La(tta) 4 - tba + ≅ Eu(tta) 4 - tba + > Lu(tta) 4 - tba + . This is similar to those of adduct metal chelates of Htta with tributylphosphate (TBP) in synergistic extraction systems. (author)

Research on the actinide chemistry in Nuclear Fuel Cycle

Energy Technology Data Exchange (ETDEWEB)

Song, Kyseok; Park, Yong Joon; Cho, Young Hwan; and others

2012-04-15

Fundamental technique to measure chemical behaviors and properties of lanthanide and actinide in radioactive waste is necessary for the development of pryochemical process. First stage, the electrochemical/spectroscopic integrated measurement system was designed and set up for spectro-electrochemical measurements of lanthanide and actinide ions in high temperature molten salt media. A compact electrochemical cell and electrode system was also developed for the minimization of reactants, and consequently minimization of radioactive waste generation. By applying these equipments, oxidation and reduction behavior of lanthanide and actinide ions in molten salt media have been made. Also, thermodynamic parameter values are determined by interpreting the results obtained from electrochemical measurements. Several lanthanide ions exhibited fluorescence properties in molten salt. Also, UV-VIS measurement provided the detailed information regarding the oxidation states of lanthanide and actinide ions in high temperature molten salt media. In the second stage, measurement system for physical properties at pyrochemical process such as viscosity, melting point and conductivity is established, and property database at different compositions of lanthanide and actinide is collected. And, both interactions between elements and properties with different potential are measured at binary composition of actinide-lanthanide in molten salt using electrochemical/spectroscopic integrated measurement system.

Application of multi-step excitation schemes for detection of actinides and lanthanides in solutions by luminescence/chemiluminescence laser spectroscopy

Energy Technology Data Exchange (ETDEWEB)

Izosimov, I. [Joint Institute for Nuclear Research, Joliot Curie 6, Dubna 141980 (Russian Federation)

2016-07-01

The use of laser radiation with tunable wavelength allows the selective excitation of actinide/lanthanide species with subsequent registration of luminescence/chemiluminescence for their detection. This work is devoted to applications of the time-resolved laser-induced luminescence spectroscopy and time-resolved laser-induced chemiluminescence spectroscopy for the detection of lanthanides and actinides. Results of the experiments on U, Eu, and Sm detection by TRLIF (Time Resolved Laser Induced Fluorescence) method in blood plasma and urine are presented. Data on luminol chemiluminescence in solutions containing Sm(III), U(IV), and Pu(IV) are analyzed. It is shown that appropriate selectivity of lanthanide/actinide detection can be reached when chemiluminescence is initiated by transitions within 4f- or 5f-electron shell of lanthanide/actinide ions corresponding to the visible spectral range. In this case chemiluminescence of chemiluminogen (luminol) arises when the ion of f element is excited by multi-quantum absorption of visible light. The multi-photon scheme of chemiluminescence excitation makes chemiluminescence not only a highly sensitive but also a highly selective tool for the detection of lanthanide/actinide species in solutions. (author)

Sigma Team for Advanced Actinide Recycle FY2015 Accomplishments and Directions

Energy Technology Data Exchange (ETDEWEB)

Moyer, Bruce A. [Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)

2015-09-30

The Sigma Team for Minor Actinide Recycle (STAAR) has made notable progress in FY 2015 toward the overarching goal to develop more efficient separation methods for actinides in support of the United States Department of Energy (USDOE) objective of sustainable fuel cycles. Research in STAAR has been emphasizing the separation of americium and other minor actinides (MAs) to enable closed nuclear fuel recycle options, mainly within the paradigm of aqueous reprocessing of used oxide nuclear fuel dissolved in nitric acid. Its major scientific challenge concerns achieving selectivity for trivalent actinides vs lanthanides. Not only is this challenge yielding to research advances, but technology concepts such as ALSEP (Actinide Lanthanide Separation) are maturing toward demonstration readiness. Efforts are organized in five task areas: 1) combining bifunctional neutral extractants with an acidic extractant to form a single process solvent, developing a process flowsheet, and demonstrating it at bench scale; 2) oxidation of Am(III) to Am(VI) and subsequent separation with other multivalent actinides; 3) developing an effective soft-donor solvent system for An(III) selective extraction using mixed N,O-donor or all-N donor extractants such as triazinyl pyridine compounds; 4) testing of inorganic and hybrid-type ion exchange materials for MA separations; and 5) computer-aided molecular design to identify altogether new extractants and complexants and theory-based experimental data interpretation. Within these tasks, two strategies are employed, one involving oxidation of americium to its pentavalent or hexavalent state and one that seeks to selectively complex trivalent americium either in the aqueous phase or the solvent phase. Solvent extraction represents the primary separation method employed, though ion exchange and crystallization play an important role. Highlights of accomplishments include: Confirmation of the first-ever electrolytic oxidation of Am(III) in a

Solvation and complexation study by fluorescence spectroscopy of Eu(III) and Cm(III) ions in octanol solution and at the interface with water

International Nuclear Information System (INIS)

Vu, T.H.

2008-01-01

Polydentate N-donors ligands like bis-triazine-pyridine (BTP) and bis-triazine-bis-pyridine (BTBP) can selectively extract minor actinides (III) from lanthanides (III) ions and therefore have been studied in the field of nuclear waste reprocessing. The aim of the researches carried out during this thesis is a better description of this family in biphasic systems: speciation in the organic phase and around the interfacial area. After an exhaustive description of the solvation of europium(III) cation in mixed solutions n-octanol water with TRLIF spectrometry, the complexation with nitrogen ligands iPr-BTP, C5-BTBP and CyMe4-BTBP has been studied by TRLIF and ESI-MS techniques. For each compound, the inner sphere of europium has been described and the conditional stability constants determined. The composition of the organic medium, and particularly the hydration degree of n-octanol, has an impact on the nature and the ratio of species 'cation - counter ion - ligand - water'. With high water content (representative of extraction systems), the complexes observed with Cm(III) and Eu(III) have the same stoichiometry but the affinity towards the curium cation is higher and consistent to separation factors measured with biphasic systems. The method TIRF (total internal reflection fluorescence) was retained to study the behaviour of europium(III) inside the interfacial area. Fluorescence spectra of europium have been obtained but side signals and the high depth resolution of detection lead to difficulty in obtaining the signal of interfacial europium alone. The selected technique remains promising but some improvements need to be implemented for forthcoming measurement at liquid/liquid interface. (author) [fr

Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

International Nuclear Information System (INIS)

Daldon, M.

1999-01-01

The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd 3+ ] [NO 3 - ] 3 [diamide] 1 , - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

Actinide-specific complexing agents: their structural and solution chemistry

International Nuclear Information System (INIS)

Raymond, K.N.; Freeman, G.E.; Kappel, M.J.

1983-07-01

The synthesis of a series of tetracatecholate ligands designed to be specific for Pu(IV) and other actinide(IV) ions has been achieved. Although these compounds are very effective as in vivo plutonium removal agents, potentiometric and voltammetric data indicate that at neutral pH full complexation of the Pu(IV) ion by all four catecholate groups does not occur. Spectroscopic results indicate that the tetracatecholates, 3,4,3-LICAMS and 3,4,3-LICAMC, complex Am(III). The Am(IV)/(III)-catecholate couple (where catecholate = 3,4,3-LICAMS or 3,4,3-LICAMC) is not observed, but may not be observable due to the large currents associated with ligand oxidation. However, within the potential range where ligand oxidation does not occur, these experiments indicate that the reduction potential of free Am(IV)/(III) is probably greater than or equal to + 2.6 V vs NHE or higher. Proof of the complexation of americium in the trivalent oxidation state by 3,4,3-LICAMS and 3,4,3-LICAMC elimates the possibility of tetracatholates stabilizing Am(IV) in vivo

Supercritical Carbon Dioxide-Soluble Ligands for Extracting Actinide Metal Ions from Porous Solids

International Nuclear Information System (INIS)

Dietz, Mark L.

2001-01-01

Numerous types of actinide-bearing waste materials are found throughout the DOE complex. Most of these wastes consist of large volumes of non-hazardous materials contaminated with relatively small quantities of actinide elements. Separation of these wastes into their inert and radioactive components would dramatically reduce the costs of stabilization and disposal. For example, the DOE is responsible for decontaminating concrete within 7000 surplus contaminated buildings. The best technology now available for removing surface contamination from concrete involves removing the surface layer by grit blasting, which produces a large volume of blasting residue containing a small amount of radioactive material. Disposal of this residue is expensive because of its large volume and fine particulate nature. Considerable cost savings would result from separation of the radioactive constituents and stabilization of the concrete dust. Similarly, gas diffusion plants for uranium enrichment contain valuable high-purity nickel in the form of diffusion barriers. Decontamination is complicated by the extremely fine pores in these barriers, which are not readily accessible by most cleaning techniques. A cost-effective method for the removal of radioactive contaminants would release this valuable material for salvage. The objective of this project is to develop novel, substituted diphosphonic acid ligands that can be used for supercritical carbon dioxide extraction of actinide ions from solid wastes. Specifically, selected diphosphonic acids, which are known to form extremely stable complexes with actinides in aqueous and organic solution, are to be rendered carbon dioxide-soluble by the introduction of appropriate alkyl- or silicon-containing substituents. The metal complexation chemistry of these new ligands in SC-CO2 will then be investigated and techniques for their use in actinide extraction from porous solids developed

Partitioning-separation of metal ions using heterocyclic ligands

International Nuclear Information System (INIS)

Hudson, M.J.; Drew, M.G.B.; Iveson, P.B.; Russell, M.L.

2001-01-01

Some guidelines are proposed for the effective design of heterocyclic ligands for partitioning because there is no doubt that the correct design of a molecular extractant is required for the effective separation of metal ions such as actinides(III) from lanthanides(III). Heterocyclic ligands with aromatic ring systems have a rich chemistry, which is only now becoming sufficiently well understood in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-carboxy-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with lanthanide ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazole-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. (author)

Multi-podant diglycolamides and room temperature ionic liquid impregnated resins: An excellent combination for extraction chromatography of actinides.

Science.gov (United States)

Gujar, R B; Ansari, S A; Verboom, W; Mohapatra, P K

2016-05-27

Extraction chromatography resins, prepared by impregnating two multi-podant diglycolamide ligands, viz. diglycolamide-functionalized calix[4]arene (C4DGA) and tripodal diglycolamide (T-DGA) dissolved in the room temperature ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethanesulfonyl)amide (RTIL: C4mimTf2N) on Chromosorb-W (an inert solid support), gave excellent results for the removal of trivalent actinides from acidic waste solutions. Distribution coefficient measurements on several metal ions showed selective sorption of Am(III) over hexavalent uranyl ions and other fission product elements such as strontium and cesium. The sorbed metal ions could be efficiently desorbed with a complexing solution containing guanidine carbonate and EDTA buffer. The sorption of Am(III) on both resins followed pseudo-second order rate kinetics with rate constants of 1.37×10(-6) and 6.88×10(-7)g/cpmmin for T-DGA and C4DGA resins, respectively. The metal sorption on both resins indicated the Langmuir monolayer chemisorption phenomenon with Eu(III) sorption capacities of 4.83±0.21 and 0.52±0.05mg per g of T-DGA and C4DGA resins, respectively. The results of column studies show that these resins are of interest for a possible application for the recovery of hazardous trivalent actinides from dilute aqueous solutions. Copyright © 2016 Elsevier B.V. All rights reserved.

Interaction of thorium with human blood proteins: relevance to the development of strategies for actinide decorporation

International Nuclear Information System (INIS)

Ali, Manjoor; Kumar, Amit; Pandey, Badri N.

2016-01-01

Thorium-232 (Th), a naturally-available actinide is emerging as an alternative source of nuclear fuel for energy generation in India and other countries. Therefore, understanding the biological interaction of Th and other lanthanides (Ln) related to Th fuel cycle would enable its efficient utilization with adequate human health and environmental protection. Studies on complexation behavior of Th with human blood proteins would yield a rationale insight for the development of potential chelation based strategies for decorporation of Th. Present study was carried out to characterize the site of interaction of Th/other Ln ions with the two most abundant protein of blood, human serum albumin (HSA) and hemoglobin (Hb). Using various spectroscopic techniques (UV-VIS, FT-IR, Raman, Fluorescence and Circular dichroism), results showed that Th interacts with carbonyl/amide groups of HSA and alters its secondary conformation. These effects of Th were compared with U and Ln ions. Comparing the structural/protein unfolding effects of these metals, ionic potential of metal ions seemed to determine their toxic action at protein level. In blood, Hb is the most abundant Fe-containing protein, transporting oxygen to the various parts of the body. Th and other metal ions were found to interact with peptide and heme sites of Hb depending upon the concentration. Results elucidated that the metal ions,Th and Ce(IV), which charge-ionic-radii-ratio are close to Fe(III), affected heme significantly as compared to metal ions of lower or higher charge-ionic-radii-ratio (La(III), Ce(III) and U(VI)). These results were found consistent to the effect of Th and Ce(IV) on oxygen-binding ability of Hb. In addition, deeper insight about binding characteristics of Th with HSA and Hb would have important implications for the development of decorporating agents for the biomedical management of actinides-induced toxicity. (author)

Study of extraction kinetics of lanthanides(III) and actinides(III) nitrates by the molecule N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide; Etude des cinetiques d'extraction des nitrates de lanthanides (III) et d'actinides (III) par le malonamide N, N'-dimethyl-N, N'-dibutyl, tetradecylmalonamide

Energy Technology Data Exchange (ETDEWEB)

Daldon, M

1999-07-01

The kinetics of extraction of lanthanides (III) and actinides (III) nitrates by the molecule N, N'-dimethyl - N, N'-dibutyl tetra-decyl malonamide has been investigated. This study was realised with a new constant interfacial-area-stirred cell. During the qualification step of the device it appears that the reduction of the device can lead to hydrolytic perturbations. The main conclusions are: - after the determination of conditions which provide kinetics regime (diffusion of species neglectable), partial orders of the kinetics law have been obtained and lead to the establishment of the law J = k [Nd{sup 3+}] [NO{sub 3}{sup -}]{sup 3} [diamide]{sup 1}, - interfacial tension measurements and kinetics study in presence of surface-active compounds proved that the chemical limiting reaction for Nd(III) is interfacial, - the results allow to propose an adsorption-desorption reaction mechanism, - a comprehensive study of the extraction kinetics of the lanthanides(III) series and also Am(III) and Cm(III) nitrates has been realised. The lighter lanthanides (La, Ce and Pr) exhibit higher kinetics rate of extraction than the others, which differs from the tendency observed with distribution coefficients which exhibit tetrad effect. The kinetics rate of extraction of Am(III) and Cm(III) is closed to the value of Eu(III). (author)

Ground-state electronic structure of actinide monocarbides and mononitrides

DEFF Research Database (Denmark)

Petit, Leon; Svane, Axel; Szotek, Z.

2009-01-01

The self-interaction corrected local spin-density approximation is used to investigate the ground-state valency configuration of the actinide ions in the actinide monocarbides, AC (A=U,Np,Pu,Am,Cm), and the actinide mononitrides, AN. The electronic structure is characterized by a gradually increa...

Synthesis and Evaluation of new Polyfunctional Molecules for Group Actinide Extraction

International Nuclear Information System (INIS)

Marie, C.

2009-10-01

The aim of this project is to design new extracting molecules for spent nuclear fuel reprocessing. In order to minimize the long-term residual radiotoxicity of the waste, the GANEX process is an option based on homogeneous recycling of actinides. All actinides (U, Np, Pu, Am, Cm), present in a highly acidic aqueous solution, would be extracted together and separated from fission products (especially from lanthanides) using liquid-liquid extraction. In this context, twenty new bi-topic ligands constituted of a nitrogen poly-aromatic unit functionalized by amide groups were synthesized. Liquid-liquid extraction tests with these ligands dissolved alone in the organic phase show that N, N, N', N'-tetra-alkyl-6, 6''(2, 2':6', 2''-terpyridine)-diamides are able to selectively extract actinides at different oxidation states (Np(V et VI), U(VI), Pu(IV), Am(III), Cm(III)) from an aqueous solution 3M HNO 3 . Nevertheless, actinides(III) are poorly extracted. According to crystallographic structures of complexes with Nd(III) and U(VI) determined by X-rays diffraction, these ligands are penta-dentate. In solution (methanol), complexes stoichiometries (1:1) of Nd(III), U(VI) and Pu(IV) were determined by electro-spray ionization mass spectrometry. Stability constants, evaluated by UV-visible spectrophotometry in MeOH/H 2 O solutions, confirm the selectivity of ligands toward actinides(III) with respect to lanthanides(III). Associate to nuclear magnetic resonance experiments and DFT calculations (Density Functional Theory), a better knowledge of their coordination mode was achieved. (author)

Effects of Ligands on a Ternary Hydroxo Complex Formation with Eu(III) in a Aqueous Solution: Comparison of a Pyridine-2,6-dicarboxylate with a Phthalate

International Nuclear Information System (INIS)

Park, K. K.; Cho, H. R.; Kim, W. H.; Jung, E. C.

2008-01-01

The interaction of a radionuclide with ligands in a groundwater influences its migration through a hydrogeological system due to a change in the characteristics of a dissolution and a sorption. Actinide ions are classified as a hard acid and strongly interact with ligands having an oxygen donor atom of a hard base such as a hydroxide, carbonate and carboxylate. These ligands reveal a large ionic bonding character. A number of experimental results on a binary complex formation of actinides have been reported. However, actinides may easily form a ternary complex by interacting simultaneously with two different ligands, since an ionic bonding does not restrict the spatial orientation of a ligand. In previous studies, a ternary hydroxo complex formation was investigated by using pyridine-2,6-dicarboxylate (PDA) or phthalate as an organic ligand and Eu(III) as an analogue of an actinide(III) ion. Although these organic ligands equally contain two carboxylate groups that interact with an Eu(III) ion, their stabilities reveal big differences. PDA is a tridentate ligand forming two 5-membered chelates, while phthalate is a bidentate ligand forming a 7-membered chelate. The latter reveals a lower stability than the former due to an angle strain. This is one of the reasons for the lower stability of the Eu(III)-phthalate than that of the Eu(III)- PDA. The difference in the stabilities of binary complexes, EuL + (L=organic ligand), influences the stabilities of the ternary hydroxo complexes, Eu(OH)L. The coordination of a phenylic or pyridine ligand can greatly enhance the fluorescence of an Eu(III) ion due to the high absorbance of a ligand by a π → π * transition and the transfer of this energy to an Eu(III) ion. These fluorescence characteristics in a binary complex system could be changed in a ternary complex. In this study, the effect of a ligand on the stability of a ternary hydroxo complex is reported by comparing the stabilities of Eu-PDA with Eu-phthalate systems

Innovative SANEX process for trivalent actinides separation from PUREX raffinate

International Nuclear Information System (INIS)

Sypula, Michal

2013-01-01

Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF Ln/Am obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as a Zr

Innovative SANEX process for trivalent actinides separation from PUREX raffinate

Energy Technology Data Exchange (ETDEWEB)

Sypula, Michal

2013-07-01

Recycling of nuclear spent fuel and reduction of its radiotoxicity by separation of long-lived radionuclides would definitely help to close the nuclear fuel cycle ensuring sustainability of the nuclear energy. Partitioning of the main radiotoxicity contributors followed by their conversion into short-lived radioisotopes is known as partitioning and transmutation strategy. To ensure efficient transmutation of the separated elements (minor actinides) the content of lanthanides in the irradiation targets has to be minimised. This objective can be attained by solvent extraction using highly selective ligands that are able to separate these two groups of elements from each other. The objective of this study was to develop a novel process allowing co-separation of minor actinides and lanthanides from a high active acidic feed solution with subsequent actinide recovery using just one cycle, so-called innovative SANEX process. The conditions of each step of the process were optimised to ensure high actinide separation efficiency. Additionally, screening tests of several novel lipophilic and hydrophilic ligands provided by University of Twente were performed. These tests were aiming in better understanding the influence of the extractant structural modifications onto An(III)/Ln(III) selectivity and complexation properties. Optimal conditions for minor actinides separation were found and a flow-sheet of a new innovative SANEX process was proposed. Tests using a single centrifugal contactor confirmed high Eu(III)/Am(III) separation factor of 15 while the lowest SF{sub Ln/Am} obtained was 6,5 (for neodymium). In addition, a new masking agent for zirconium was found as a substitution for oxalic acid. This new masking agent (CDTA) was also able to mask palladium without any negative influence on An(III)/Ln(III). Additional tests showed no influence of CDTA on plutonium present in the feed solution unlike oxalic acid which causes Pu precipitation. Therefore, CDTA was proposed as

Complexes in solution of o-phenanthroline with the ions of 4f and 5f elements at valencies II, III, V, VI

International Nuclear Information System (INIS)

Le Marois, Gilles.

1980-06-01

Slight differences between the complexation in aqueous solution of 4f and 5f series ions are revealed by the use of a soft, aromatic and chelating ligand of the o-phenanthroline type. Trivalent actinide ions are extrated selectively in the presence of a carboxylic acid. This extraction takes place at high pH and does not require large quantities of salts in aqueous solution, which increase the volume of radioactive wastes for storage. Only the first two o-phenanthroline complexes of these ions are obtained in aqueous solution. Determination of the constants of formation of such complexes shows the stronger affinity of the ligand for actinide ions. An inversion of the usual order of complexation of the different actinide valencies is also observed: pentavalent ions are most complexed than trivalent, o-phenanthroline stabilises actinide ions preferentially because they are more liable to form bonds with delocalised electrons. Finally a slight stabilisation of europium at valency II shows the participation of electrons by back bonding of the metal, due to the strong conjugation of the ligand π electrons [fr

Inner-sphere and outer-sphere complexes of yttrium(III), lanthanum (III), neodymium(III), terbium(III) and thulium(III) with halide ions in N,N-dimethylformamide

International Nuclear Information System (INIS)

Takahashi, Ryouta; Ishiguro, Shin-ichi

1991-01-01

The formation of chloro, bromo and iodo complexes of yttrium(III), and bromo and iodo complexes of lanthanum(III), neodymium(III), terbium(III) and thulium(III) has been studied by precise titration calorimetry in N,N-dimethylformamide (DMF) at 25 o C. The formation of [YCl] 2+ , [YCl 2 ] + , [YCl 3 ] and [YCl 4 ] - , and [MBr] 2+ and [MBr 2 ] + (M = Y, La, Nd, Tb, Tm) was revealed, and their formation constants, enthalpies and entropies were determined. It is found that the formation enthalpies change in the sequence ΔH o (Cl) > ΔH o (l), which is unusual for hard metal (III) ions. This implies that, unlike the chloride ion, the bromide ion forms outer-sphere complexes with the lanthanide(III) and yttrium(III) ions in DMF. Evidence for either an inner- or outer-sphere complex was obtained from 89 Y NMR spectra for Y(ClO 4 ) 3 , YCl 3 and YBr 3 DMF solutions at room temperature. (author)

Chemistry of actinides and fission products

International Nuclear Information System (INIS)

Pruett, D.J.; Sherrow, S.A.; Toth, L.M.

1988-01-01

This task is concerned primarily with the fundamental chemistry of the actinide and fission product elements. Special efforts are made to develop research programs in collaboration with researchers at universities and in industry who have need of national laboratory facilities. Specific areas currently under investigation include: (1) spectroscopy and photochemistry of actinides in low-temperature matrices; (2) small-angle scattering studies of hydrous actinide and fission product polymers in aqueous and nonaqueous solvents; (3) kinetic and thermodynamic studies of complexation reactions in aqueous and nonaqueous solutions; and (4) the development of inorganic ion exchange materials for actinide and lanthanide separations. Recent results from work in these areas are summarized here

Sorption of plutonium and curium on ion exchange resins in mixed aqueous organic solutions

International Nuclear Information System (INIS)

Haidvogel, N.; Reitsamer, G.; Grass, F.

1974-12-01

The sorption of the sulfate and nitrate-complexes of the actinides Pu(III), Pu(IV), Pu(VI), Am(III) and Om(III) on the ion-exchange-resins Dowex 1X8 and Dowex 50 WX8 is investigated. The strong sorbability of these actinide ions in solvents with high content of alcohol is explained by the existence of anionic complexes like Pu(III) (SO 4 ) 2 - , Pu(IV) (SO 4 ) 3 2 - , Pu(VI)O 2 (SO 4 ) 2 2 - , Am(SO 4 ) 2 - respectively Am(NO 3 ) 4 - and Om(NO 3 ) 4 - . The taking of autoradiographs from the thin-layer chromatograms by the aid of a special device and the evaluation of the autoradiographs by a particular photodensitometer are described. The measurement of the radioactivity of the α-emitting nuclides Pu 239, Am 241 and Om 242 are done by liquid-scintillation spectrometry. (author)

MICROBIAL IMPACTS ON THE MIGRATION OF ACTINIDES -EFFECTS OF EXUDATES ON ADSORPTION-

International Nuclear Information System (INIS)

OHNUKI, T.; OZAKI, T.; YOSHIDA, T.; NANKAWA, T.; KOZAI, N.; SAKAMOTO, F.; SUZUKI, Y.; FRANCIS, A.J.

2006-01-01

The interaction of actinides with microorganisms has been extensively studied to elucidate migration behavior of actinides in the environments. However, the mechanisms of interaction of microorganisms and actinides are poorly understood. They have been conducting basic science on microbial accumulation of actinides in order to elucidate the environmental behavior of actinides under relevant conditions. The effect of exudates from bacteria cells on the sorption of Eu(III) and Cm(III) by Chlorella vulgaris was studied by a batch method. The pH dependence of log K d of Eu(III) and Cm(III) for cellulose, major component of C. vulgaris cell, differed from that for C. vulgaris. On the contrary, log K d of Eu(III) and Cm(III) for cellulose in the solution containing exudates from C. vulgaris cells in a 0.5% NaCl solution showed a similar pH dependence to that by C. vulgaris. These results strongly suggested that exudates affect on the sorption of Eu(III) and Cm(III) on C. vulgaris. Effect of desferrioxamine B (DFO), one of exudates to chelate the insoluble Fe(III), on the sorption of Pu(IV), Th(IV) and Eu(III) by Pseudomonas fluorescens was studied. In the presence of DFO the sorption of Pu(IV), Th(IV) and Eu(III) on the cells increased with a decrease in pH from 7 to 4. In contrast, without DFO most of Pu(IV), Th(IV) and Eu(III) were precipitated from solution. Adsorption of DFO on the cells was negligible in the solution with and without metals. Adsorption of Pu(IV), Th(IV) and Eu(III) on P. fluorescens cells decreased in the order Eu(III) > Th(IV) > Pu(IV), which corresponds to increasing stability constant of the DFO complexes. These results indicate that Th(IV), Pu(IV) and Eu(III) dissociate when in contact with cells, after which the metals are adsorbed

Microbial impacts on the migration of actinides. Effects of exudates on adsorption

International Nuclear Information System (INIS)

Ohnuki, Toshihiko; Ozaki, Takuo; Nakawa, Takuya; Kozai, Naofumi; Sakamoto, Fuminori; Suzuki, Yosinori; Yoshida, Takahiro; Francis, Arokiasamy J.

2007-01-01

The interaction of actinides with microorganisms has been extensively studied to elucidate migration behavior of actinides in the environments. However, the mechanisms of interaction of microorganisms and actinides are poorly understood. We have been conducting basic science on microbial accumulation of actinides in order to elucidate the environmental behavior of actinides under relevant conditions. The effect of exudates from bacteria cells on the sorption of Eu(III) and Cm(III) by Chlorella vulgaris was studied by a batch method. The pH dependence of log K d of Eu(III) and Cm(III) for cellulose, major component of C. vulgaris cell, differed from that for C. vulgaris. On the contrary, log K d of Eu(III) and Cm(III) for cellulose in the solution containing exudates from C. vulgaris cells in a 0.5% NaCl solution showed a similar pH dependence to that by C. vulgaris. These results strongly suggested that exudates affect on the sorption of Eu(III) and Cm(III) on C. vulgaris. Effect of desferrioxamine B (DFO), one of exudates to chelate with insoluble Fe(III), on the sorption of Pu(IV), Th(IV) and Eu(III) by Pseudomonas fluorescens was studied. In the presence of DFO the sorption of Pu(IV), Th(IV) and Eu(III) on the cells increased with a decrease in pH from 7 to 4. In contrast, without DFO most of Pu(IV), Th(IV) and Eu(III) were precipitated from solution. Adsorption of DFO on the cells was negligible in the solution with and without metals. Adsorption of Pu(IV), Th(IV) and Eu(III) on P. fluorescens cells decreased in the order Eu(III) > Th(IV) > Pu(IV), which corresponds to increasing stability constant of the DFO complexes. These results indicate that Th(IV), Pu(IV) and Eu(III) dissociate when in contact with cells, after which the metals are adsorbed. (author)

Design, synthesis, and evaluation of polyhydroxamate chelators for selective complexation of actinides

International Nuclear Information System (INIS)

Gopalan, A.; Jacobs, H.; Koshti, N.; Stark, P.; Huber, V.; Dasaradhi, L.; Caswell, W.; Smith, P.; Jarvinen, G.

1995-01-01

Specific chelating polymers targeted for actinides have much relevance to problems involving remediation of nuclear waste. Goal is to develop polymer supported, ion specific extraction systems for removing actinides and other hazardous metal ions from wastewaters. This is part of an effort to develop chelators for removing actinide ions such as Pu from soils and waste streams. Selected ligands are being attached to polymeric backbones to create novel chelating polymers. These polymers and other water soluble and insoluble polymers have been synthesized and are being evaluated for ability to selectively remove target metal ions from process waste streams

Complexation of trivalent actinides and lanthanides with hydrophilic N-donor ligands for Am(III)/Cm(III) and An(III)/Ln(III) separation; Komplexierung von trivalenten Actiniden und Lanthaniden mit hydrophilen N-Donorliganden zur Am(III)/Cm(III)- bzw. An(III)/Ln(III)-Trennung

Energy Technology Data Exchange (ETDEWEB)

Wagner, Christoph

2017-07-24

The implementation of actinide recycling processes is considered in several countries, aiming at the reduction of long-term radiotoxicity and heat load of used nuclear fuel. This requires the separation of the actinides from the fission and corrosion products. The separation of the trivalent actinides (An(III)) Am(III) and Cm(III), however, is complicated by the presence of the chemically similar fission lanthanides (Ln(III)). Hydrophilic N-donor ligands are employed as An(III) or Am(III) selective complexing agents in solvent extraction to strip An(III) or Am(III) from an organic phase loaded with An(III) and Ln(III). Though they exhibit excellent selectivity, the complexation chemistry of these ligands and the complexes formed during solvent extraction are not sufficiently characterized. In the present thesis the complexation of An(III) and Ln(III) with hydrophilic N-donor ligands is studied by time resolved laser fluorescence spectroscopy (TRLFS), UV/Vis, vibronic sideband spectroscopy and solvent extraction. TRLFS studies on the complexation of Cm(III) and Eu(III) with the Am(III) selective complexing agent SO{sub 3}-Ph-BTBP (tetrasodium 3,3{sup '},3'',3{sup '''}-([2,2{sup '}-bipyridine]-6,6{sup '}-diylbis(1,2,4-triazine-3,5,6-triyl)) tetrabenzenesulfonate) revealed the formation of [M(SO{sub 3}-Ph-BTBP){sub n}]{sup (4n-3)-} complexes (M = Cm(III), Eu(III); n = 1, 2). The conditional stability constants were determined in different media yielding two orders of magnitude larger β{sub 2}-values for the Cm(III) complexes, independently from the applied medium. A strong impact of ionic strength on the stability and stoichiometry of the formed complexes was identified, resulting from the stabilization of the pentaanionic [M(SO{sub 3}-Ph-BTBP){sub 2}]{sup 5-} complex with increasing ionic strength. Thermodynamic studies of Cm(III)-SO{sub 3}-Ph-BTBP complexation showed that the proton concentration of the applied medium impacts

TUCS/phosphate mineralization of actinides

Energy Technology Data Exchange (ETDEWEB)

Nash, K.L. [Argonne National Lab., IL (United States)

1997-10-01

This program has as its objective the development of a new technology that combines cation exchange and mineralization to reduce the concentration of heavy metals (in particular actinides) in groundwaters. The treatment regimen must be compatible with the groundwater and soil, potentially using groundwater/soil components to aid in the immobilization process. The delivery system (probably a water-soluble chelating agent) should first concentrate the radionuclides then release the precipitating anion, which forms thermodynamically stable mineral phases, either with the target metal ions alone or in combination with matrix cations. This approach should generate thermodynamically stable mineral phases resistant to weathering. The chelating agent should decompose spontaneously with time, release the mineralizing agent, and leave a residue that does not interfere with mineral formation. For the actinides, the ideal compound probably will release phosphate, as actinide phosphate mineral phases are among the least soluble species for these metals. The most promising means of delivering the precipitant would be to use a water-soluble, hydrolytically unstable complexant that functions in the initial stages as a cation exchanger to concentrate the metal ions. As it decomposes, the chelating agent releases phosphate to foster formation of crystalline mineral phases. Because it involves only the application of inexpensive reagents, the method of phosphate mineralization promises to be an economical alternative for in situ immobilization of radionuclides (actinides in particular). The method relies on the inherent (thermodynamic) stability of actinide mineral phases.

Hydration of the lanthanide ions 152Eu(III), 153Gd(III) and 170Tm(III) in aqueous solutions at 298 K and similarity with the transplutonium element ions 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III)

International Nuclear Information System (INIS)

Ouerfelli, N.; Latrous, H.; Ammar, M.; Das, D.; Oliver, J.

2013-01-01

The open-end capillary method is used for the determination of ionic self-diffusion coefficients (D) for trivalent radiotracer, lanthanide and actinide ions are reported in concentrated aqueous solutions of supporting electrolytes of Gd(NO 3 ) 3 -HNO 3 or Nd(ClO 3 ) 4 -HClO 4 up to 1.5 mol.L -1 at 298.15 K and pH 2.50. The data obtained in large range of concentrations, allow deriving the limiting value D°, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. (author)

The chemistry of the actinide elements. Volume I

International Nuclear Information System (INIS)

Katz, J.J.; Seaborg, G.T.; Morss, L.R.

1986-01-01

The Chemistry of the Actinide Elements is a comprehensive, contemporary and authoritative exposition of the chemistry and related properties of the 5f series of elements: actinium, thorium, protactinium, uranium and the first eleven. This second edition has been completely restructured and rewritten to incorporate current research in all areas of actinide chemistry and chemical physics. The descriptions of each element include accounts of their history, separation, metallurgy, solid-state chemistry, solution chemistry, thermo-dynamics and kinetics. Additionally, separate chapters on spectroscopy, magnetochemistry, thermodynamics, solids, the metallic state, complex ions and organometallic compounds emphasize the comparative chemistry and unique properties of the actinide series of elements. Comprehensive lists of properties of all actinide compounds and ions in solution are given, and there are special sections on such topics as biochemistry, superconductivity, radioisotope safety, and waste management, as well as discussion of the transactinides and future elements

Extraction chromatographic method for the separation of actinides and lanthanides using EDHBA grafted AXAD-16 polymer

Energy Technology Data Exchange (ETDEWEB)

Akhila Maheswari, M.; Subramanian, M.S. [Department of Chemistry, Indian Institute of Technology, Chennai (India)

2005-02-15

A new extraction chromatographic method has been developed by grafting chloromethylated polymer support with 4-ethoxy-N,N-dihexylbutanamide (EDHBA), for the selective extraction of U(VI), Th(IV), La(III) and Nd(III) from highly acidic matrices. The developed grafted polymer has been characterized using {sup 13}C-CPMAS NMR spectroscopy, FT-NIR spectroscopy and also by CHN elemental analysis. The water regaining capacity of the grafted polymer is studied by TGA measurements and the active participation of the amide moiety towards metal ion complexation has been confirmed by Far IR spectroscopy. For the quantitative extraction of metal ions to the resin phase, various physico-chemical parameters are optimized by both static and dynamic methods. The developed amide grafted polymeric matrix shows good distribution ratio values even at high acidities, with the maximum metal sorption capacity values being 0.36, 0.69, 0.32 and 0.42mmolg{sup -1} for U(VI), Th(IV), La(III) and Nd(III), respectively, at 6M HNO{sub 3} medium. The kinetics of metal ion phase equilibration is found to be moderately fast, with t{sub 1/2} values of <6min, for all the analytes of interest. The limits of analyte quantification (LOQ) using the developed method are in the range of 15-30{mu}gL{sup -1}. Moreover, the sequential separation of the sorbed actinides and lanthanides could be achieved by first eluting with 100mL of distilled water (for actinides) followed by elution with 20mL of 0.1M EDTA (for lanthanides). The selectivity behavior and the practical applicability of the developed resin are tested using synthetic low level nuclear reprocessing mixtures and also with monazite sand. The analytical data are within 3.8% relative standard deviation, reflecting the reproducibility and reliability of the developed method.

Actinide metals

Energy Technology Data Exchange (ETDEWEB)

Brown, Paul L. [Geochem Australia, Kiama, NSW (Australia); Ekberg, Christian [Chalmers Univ. of Technology, Goeteborg (Sweden). Nuclear Chemistry/Industrial Materials Recycling

2016-07-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO{sub 2}OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH{sup 2+} for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Actinide metals

International Nuclear Information System (INIS)

Brown, Paul L.; Ekberg, Christian

2016-01-01

All isotopes of actinium are radioactive and exist in aqueous solution only in the trivalent state. There have been very few studies on the hydrolytic reactions of actinium(III). The hydrolysis reactions for uranium would only be important in alkaline pH conditions. Thermodynamic parameters for the hydrolysis species of uranium(VI) and its oxide and hydroxide phases can be determined from the stability and solubility constants. The hydrolytic behaviour of neptunium(VI) is quite similar to that of uranium(VI). The solubility constant of NpO 2 OH(am) has been reported a number of times for both zero ionic strength and in fixed ionic strength media. Americium can form four oxidation states in aqueous solution, namely trivalent, tetravalent, pentavalent and hexavalent. Desire, Hussonnois and Guillaumont determined stability constants for the species AmOH 2+ for the actinides, plutonium(III), americium(III), curium(III), berkelium(III) and californium(III) using a solvent extraction technique.

Recent progress in actinide and lanthanide solvent extraction

International Nuclear Information System (INIS)

Musikas, C.; Hubert, H.; Benjelloun, N.; Vitorge, P.; Bonnin, M.; Forchioni, A.; Chachaty, C.

1983-04-01

Work in progress on actinide solvent extraction is briefly reviewed in this paper. 1 H and 31 P NMR are used to elucidate several fundamental unsolved problems concerning organophosphorous extractants often used in actinides extraction: determination of site of dialkylthiophosphate protonation and addition of basic phosphine oxide to dibutylthiophosphoric acid dimer. Extraction of Am III and Eu from high radioactivity level wastes by tetrasubsituted methylene diamides is investigated. Trivalent actinide-lanthanide group are separated by solvent extraction using soft donor ligand complexes which are more stable. The synergism of dinonylnaphtalene sulfonic acid (HDNNS) associated with several neutral donors like TBP, TOPO, amides are examined in the trivalent and tetravalent actinide extraction

Effects of humic substances on the migration of radionuclides: Complexation of actinides with humic substances

International Nuclear Information System (INIS)

Kim, J.I.; Rhee, D.S.; Wimmer, H.; Buckau, G.; Klenze, R.; Decambox, P.; Moulin, C.; Moulin, V.; Tits, J.; Marquardt, C.; Herrmann, G.; Trautmann, N.; Dierckx, A.; Vancluysen, J.; Maes, A.

1992-09-01

The aim of the present research programme is to study the complexation behaviour of actinide ions with humic substances in natural aquifer systems and hence to quantify the effect of humic substances on the actinide migration. Aquatic humic substances commonly found in all groundwaters in different concentrations have a strong tendency towards complexation with actinide ions. This is one of the major geochemical reactions but hitherto least quantified. Therefore, the effect of humic substances on the actinide migration is poorly understood. In the present research programme the complexation of actinide ions with humic substances will be described thermodynamically. This description will be based on a model being as simple as possible to allow an easy introduction of the resulting constants into geochemical modelling of the actinide migration. (orig.)

The electronic structure of the lanthanides and actinides, a comparison

International Nuclear Information System (INIS)

Edelstein, N.M.

1998-01-01

Full text: Optical spectra of the two f-element series (the lanthanides and actinides) are comparable in many respects. For the trivalent ions isolated in single crystals, both series exhibit rich, narrow line spectra. These data can be analysed in terms of a parametric model based on a free-ion Hamiltonian plus the addition of a crystal field Hamiltonian. For most systems the agreement between the calculated and experimental energy levels is quite good. In the actinide series there appears to be a correlation between the magnitude of the crystal field and the inadequacy of the fits. The early actinides exhibit multiple oxidation states for which there is no precedent in the lanthanide series. The parametric model mentioned earlier has been utilized for some tetravalent actinide systems with reasonably good results. A selective survey of results describing the similarities and differences of various lanthanide and actinide systems will be given

Actinide chemistry in the far field

International Nuclear Information System (INIS)

Livens, F.R.; Morris, K.; Parkman, R.; Moyes, L.

1996-01-01

The environmental chemistry of the actinides is complicated due both to the extensive redox and coordination chemistry of the elements and also to the complexity of the reactive phases encountered in natural environments. In the far field, interactions with reactive surfaces, coatings and colloidal particles will play a crucial role in controlling actinide mobility. By virtue of both their abundance and reactivity; clays and other layer aluminosilicate minerals, hydrous oxides and organic matter (humic substances) are all identified as having the potential to react with actinide ions and some possible modes of interaction are described, together with experimental evidence for their occurrence. (author)

Adsorption of actinides by chelating agents containing benzene rings, fixed on charcoal

International Nuclear Information System (INIS)

Valentini Ganzerli, M.T.; Crespi Caramella, V.; Maggi, L.

1999-01-01

The focus of this paper is on the analysis of the actinides in the hydrosphere to study their environmental dispersion. The 8-hydroxyquinoline family and the benzohydroxamic acid have a complexing ability towards the actinides, even if in different oxidation states. Taking advantage of this ability, their salts with some organic acids or bases were prepared. In this way compounds were obtained easily incorporated into active charcoal. Only a small amount of the prepared adsorber may be equilibrated with large sample volumes. Subsequently it can be recovered by filtration. The adsorbed ions may be then re-dissolved with a small volume of the appropriate eluting solution. The 8-hydroxy-quinolines and the 8-hydroxyquinoline produced salts with the benzilic acid. These compounds similarly behave and show wide adsorption coefficients for solutions of pH higher than 3. The adsorption takes place by means of the formation of a complex of the actinide ion with the hydroxyquinoline moiety and also with the benzilic anion. Provided that the active extracting agent is not dissolved in a medium but fixed into a solid phase, the whole adsorption process may be regarded as a solvent extraction reaction. The benzohydroxamic acid was treated with the diphenylamine or with the tribenzylamine to obtain salts, later adsorbed into the charcoal. The adsorption of actinide ions seems to take place by means of a precipitation mechanism of the actinide ions with the hydroxamate ions for solution of pH higher than 3.5. Also in this case high values were obtained for the distribution coefficients. The actinide ions act similarly in the +4 or +6 oxidation state towards the prepared adsorber series. Therefore, it is possible to use only one adsorber to concentrate all actinides. Methods of analysis of actinides in the environment may be suitably set up and the concentration step based on these new prepared adsorber may improve the whole procedure. (authors)

Synthesis and structural characterization of actinide oxalate compounds

International Nuclear Information System (INIS)

Tamain, C.

2011-01-01

Oxalic acid is a well-known reagent to recover actinides thanks to the very low solubility of An(IV) and An(III) oxalate compounds in acidic solution. Therefore, considering mixed-oxide fuel or considering minor actinides incorporation in ceramic fuel materials for transmutation, oxalic co-conversion is convenient to synthesize mixed oxalate compounds, precursors of oxide solid solutions. As the existing oxalate single crystal syntheses are not adaptable to the actinide-oxalate chemistry or to their manipulation constrains in gloves box, several original crystal growth methods were developed. They were first validate and optimized on lanthanides and uranium before the application to transuranium elements. The advanced investigations allow to better understand the syntheses and to define optimized chemical conditions to promote crystal growth. These new crystal growth methods were then applied to a large number of mixed An1(IV)-An2(III) or An1(IV)-An2(IV) systems and lead to the formation of the first original mixed An1(IV)-An2(III) and An1(IV)-An2(IV) oxalate single crystals. Finally thanks to the first thorough structural characterizations of these compounds, single crystal X-ray diffraction, EXAFS or micro-RAMAN, the particularly weak oxalate-actinide compounds structural database is enriched, which is essential for future studied nuclear fuel cycles. (author) [fr

Investigation of the complexation and the migration of actinides and non-radioactive substances with humic acids under geogenic conditions. Complexation of humic acids with actinides in the ocidation state IV Th, U, Np

Energy Technology Data Exchange (ETDEWEB)

Sachs, S.; Schmeide, K.; Brendler, V.; Krepelova, A.; Mibus, J.; Geipel, G.; Heise, K.H.; Bernhard, G.

2004-03-01

Objective of this project was the study of basic interaction and migration processes of actinides in the environment in presence of humic acids (HA). To obtain more basic knowledge on these interaction processes synthetic HA with specific functional properties as well as {sup 14}C-labeled HA were synthesized and applied in comparison to the natural HA Aldrich. One focus of the work was on the synthesis of HA with distinct redox functionalities. The obtained synthetic products that are characterized by significantly higher Fe(III) redox capacities than Aldrich HA were applied to study the redox properties of HA and the redox stability of U(VI) humate complexes. It was confirmed that phenolic OH groups play an important role for the redox properties of HA. However, the results indicate that there are also other processes than the single oxidation of phenolic OH groups and/or other functional groups contributing to the redox behavior of HA. A first direct-spectroscopic proof for the reduction of U(VI) by synthetic HA with distinct redox functionality was obtained. The complexation behavior of synthetic and natural HA with actinides (Th, Np, Pu) was studied. Structural parameters of Pu(III), Th(IV), Np(IV) and Np(V) humates were determined by X-ray absorption spectroscopy (XAS). The results show that carboxylate groups dominate the interaction between HA and actinide ions. These are predominant monodentately bound. The influence of phenolic OH groups on the Np(V) complexation by HA was studied with modified HA (blocked phenolic OH groups). The blocking of phenolic OH groups induces a decrease of the number of maximal available complexing sites of HA, whereas complex stability constant and Np(V) near-neighbor surrounding are not affected. The effects of HA on the sorption and migration behavior of actinides was studied in batch and column experiments. Th(IV) sorption onto quartz and Np(V) sorption onto granite and its mineral constituents are affected by the pH value

Investigation of the complexation and the migration of actinides and non-radioactive substances with humic acids under geogenic conditions. Complexation of humic acids with actinides in the oxidation state IV Th, U, Np

International Nuclear Information System (INIS)

Sachs, S.; Schmeide, K.; Brendler, V.; Krepelova, A.; Mibus, J.; Geipel, G.; Heise, K.H.; Bernhard, G.

2004-03-01

Objective of this project was the study of basic interaction and migration processes of actinides in the environment in presence of humic acids (HA). To obtain more basic knowledge on these interaction processes synthetic HA with specific functional properties as well as 14 C-labeled HA were synthesized and applied in comparison to the natural HA Aldrich. One focus of the work was on the synthesis of HA with distinct redox functionalities. The obtained synthetic products that are characterized by significantly higher Fe(III) redox capacities than Aldrich HA were applied to study the redox properties of HA and the redox stability of U(VI) humate complexes. It was confirmed that phenolic OH groups play an important role for the redox properties of HA. However, the results indicate that there are also other processes than the single oxidation of phenolic OH groups and/or other functional groups contributing to the redox behavior of HA. A first direct-spectroscopic proof for the reduction of U(VI) by synthetic HA with distinct redox functionality was obtained. The complexation behavior of synthetic and natural HA with actinides (Th, Np, Pu) was studied. Structural parameters of Pu(III), Th(IV), Np(IV) and Np(V) humates were determined by X-ray absorption spectroscopy (XAS). The results show that carboxylate groups dominate the interaction between HA and actinide ions. These are predominant monodentately bound. The influence of phenolic OH groups on the Np(V) complexation by HA was studied with modified HA (blocked phenolic OH groups). The blocking of phenolic OH groups induces a decrease of the number of maximal available complexing sites of HA, whereas complex stability constant and Np(V) near-neighbor surrounding are not affected. The effects of HA on the sorption and migration behavior of actinides was studied in batch and column experiments. Th(IV) sorption onto quartz and Np(V) sorption onto granite and its mineral constituents are affected by the pH value and the

Demonstration of innovative partitioning processes for minor actinide recycling from high active waste solutions

International Nuclear Information System (INIS)

Modolo, G.; Wilden, A.; Geist, A.; Malmbeck, R.; Taylor, R.

2014-01-01

The recycling of the minor actinides (MA) using the Partitioning and Transmutation strategy (P and T) could contribute significantly to reducing the volume of high level waste in a geological repository and to decreasing the waste's longterm hazards originating from the long half-life of the actinides. Several extraction processes have been developed worldwide for the separation and recovery of MA from highly active raffinates (HAR, e.g. the PUREX raffinate). A multi-cycle separation strategy has been developed within the framework of European collaborative projects. The multi-cycle processes, on the one hand, make use of different extractants for every single process. Within the recent FP7 European research project ACSEPT (Actinide reCycling by SEParation and Transmutation), the development of new innovative separation processes with a reduced number of cycles was envisaged. In the so-called 'innovative SANEX' concept, the trivalent actinides and lanthanides are co-extracted from the PUREX raffinate by a DIAMEX like process (e.g. TODGA). Then, the loaded solvent is subjected to several stripping steps. The first one concerns selectively stripping the actinides(III) with selective water-soluble ligands (SO3-Ph-BTB), followed by the subsequent stripping of trivalent lanthanides. A more challenging route studied also within our laboratories is the direct actinide(III) separation from a PUREX-type raffinate using a mixture of CyMe 4 BTBP and TODGA as extractants, the so-called One cycle SANEX process. A new approach, which was also studied within the ACSEPT project, is the GANEX (Grouped ActiNide EXtraction) concept addressing the simultaneous partitioning of all transuranium (TRU) elements for their homogeneous recycling in advanced generation IV reactor systems. Bulk uranium is removed in the GANEX 1st cycle, e.g. using a monoamide extractant and the GANEX 2nd cycle then separates the TRU. A solvent composed of TODGA + DMDOHEMA in kerosene has been shown to

Synergistic extraction of actinides : Part I. Hexa-and pentavalent actinides

International Nuclear Information System (INIS)

Patil, S.K.; Ramakrishna, V.V.

1980-01-01

A detailed discussion on the reported literature on the synergistic extraction of hexa- and pentavalent actinide ions, by different combinations of extractants and from different aqueous media, is presented. Structural aspects of the various complexes involved in synergism also are reviewed. A short account of the applications based on synergistic extraction is also given. (author)

Synthesis of selective extractor for minor actinide elements

Energy Technology Data Exchange (ETDEWEB)

Kim, Jong Seung [Konyang University, Nonsan (Korea); Cho, Moon Hwan [Kangwon National University, Chunchon (Korea)

1998-04-01

To selectively co-separate the lanthanide and actinide elements (MA) such as Am or Cm ion from radioactive waste, synthesis of diamide derivatives has been accomplished. In addition, picoline amide derivatives were also synthesized for selectively separate the minor actinide elements from lanthanide elements. The content of research has don are as follows: (1) synthesis of diamide as co-extractant (2) introduction of n-tetradecyl to increase the lipophilicity (3) Picolyl chloride, intermediate of the final product, was synthesized by improved method rather than reported method. (4) The length of alkyl side chain was adjusted to increase the lipophilicity of free ligand and its derivatives able to selectively separate the actinide metal from lanthanide metal ions was successfully synthesized and determined their purity by analytical instruments. (author). 12 refs., 28 figs.

A comparative study of ion exchange properties of antimony (III) tungstoselenite with those of antimony (III) tungstate and antimony (III) selenite

International Nuclear Information System (INIS)

Janardanan, C.; Nair, S.M.K.

1996-01-01

A new inorganic ion exchanger, antimony (III) tungstoselenite, has been prepared and characterised. Its exchange capacity and distribution coefficients for various metal ions and the effects of temperature and electrolyte concentrations on ion exchange capacity have been compared with antimony (III) tungstate and antimony (III) selenite. Six binary separations using the exchanger have been carried out. (author). 7 refs., 1 tab

Extraction of Am (III) and Nd (III): comparison of TODGA and TEHDGA

International Nuclear Information System (INIS)

Gujar, R.B.; Murali, M.S.; Ansari, S.A.; Manchanda, V.K.

2009-01-01

Belonging to the class of extractants, diglycolamides which are recently explored and promising for actinide partitioning, two reagents (N, N, N', N'-tetraoctyl diglycolamide) TODGA and its isomerically substituted counterpart, (N, N, N', N'- tetraethylhexyl diglycolamide) TEHDGA after addition of suitable phase modifiers, Dihexyoctanamide and isodecanol respectively in dodecane have been compared in their extraction abilities for Am (III) and Nd (III) from nitric acid as well as simulated high-level waste solutions (SHLW) equivalent to HLW arising from PHWR fuel reprocessing. Both 0.1M TODGA + 0.5M DHOA and 0.2M TEHDGA + 30% isodecanol in dodecane display high distribution ratios for the trivalent metal ions of f-elements. Similarities and differences in their extraction are discussed. (author)

New strategies for the chemical separation of actinides and lanthanides

International Nuclear Information System (INIS)

Hudson, M.J.; Iveson, P.B.

2002-01-01

A general model is proposed for the effective design of ligands for partitioning. There is no doubt that the correct design of a molecule is required for the effective separation by separation of metal ions such as lanthanides(III) and actinides(III). Heterocyclic ligands with aromatic rings systems have a rich chemistry, which is only now becoming sufficiently well understood, in relation to the partitioning process. The synthesis, characterisation and structures of some chosen molecules will be introduced in order to illustrate some important features. For example, the molecule N-butyl-2-amino-4,6-di (2-pyridyl)-1,3,5-triazine (BADPTZ), which is an effective solvent extraction reagent for actinides and lanthanides, has been synthesised, characterised and its interaction with metal ions studied. The interesting and important features of this molecule will be compared with those of other heterocyclic molecules such as 2,6-bis(5-butyl-1,2,4-triazol-3-yl) pyridine (DBTZP), which is a candidate molecule for the commercial separation of actinides and lanthanide elements. Primary Coordination Sphere. One of the most critical features concerning whether a molecule is a suitable extraction reagent is the nature of the binding and co-ordination in the primary co-ordination sphere. This effect will be considered in depth for the selected heterocylic molecules. It will be shown how the bonding of the heterocyclic and nitrate ligands changes as the complete lanthanide series is traversed from lanthanum to lutetium. For effective solvent extraction, the ligand(s) should be able completely to occupy the primary co-ordination sphere of the metal ion to be extracted. Interactions in the secondary co-ordination sphere are of less importance. Inter-complex Hydrogen Bonding Interactions. Another feature that will be considered is the intermolecular binding between ligands when bound to the metal ion. Thus the intermolecular structures between complex molecules will be considered

Ion temperatures in TORTUR III

International Nuclear Information System (INIS)

Hendriks, F.B.

1985-12-01

Spatially resolved ion-energy distributions are presented for discharges in the TORTUR III tokamak. The measurements are performed in an active method, using a neutral hydrogen probing beam of 20-30 keV, to enhance charge-exchange processes along its path, as well as by the usual passive method. Ion temperatures can amount up to 1 keV

Actinide removal from aqueous solution with activated magnetite

International Nuclear Information System (INIS)

Kochen, R.L.; Thomas, R.L.

1987-01-01

An actinide aqueous waste treatment process using activated magnetite has been developed at Rocky Flats. The use and effectiveness of various magnetites in lowering actinide concentrations in aqueous solution are described. Experiments indicate that magnetite particle size and pretreatment (activation of the magnetite surface with hydroxyl ions greatly influence the effective use of magnetite as an actinide adsorbent. With respect to actinide removal, Ba(OH) 2 -activated magnetite was more effective over a broader pH range than was NaOH-activated magnetite. About 50% less Ba(OH) 2 -activated magnetite was required to lower plutonium concentration from 10 -4 to 10 -8 g/l. 7 refs., 8 tabs

Actinide extractants for the nuclear industry of the future

International Nuclear Information System (INIS)

Musikas, C.; Morisseau, J.C.; Hoel, P.; Guillaume, B.

1987-06-01

Non organo-phosphorus extractants properties regarding the extractions of actinides in nuclear fuels reprocessing are presented. N,N-dialkylamides are proposed as alternatives to TBP.N,N'-tetraalkylamides or pentaalkyl propane diamides properties are reported. They show that those bidentate extractants are alternatives to bidentate organophosphorus extractants for actinides (III) extraction from concentrated nitric acid. 11 figs, 15 refs

SEPARATION OF Fe (III, Cr(III, Cu(II, Ni(II, Co(II, AND Pb(II METAL IONS USING POLY(EUGENYL OXYACETIC ACID AS AN ION CARRIER BY A LIQUID MEMBRANE TRANSPORT METHOD

Directory of Open Access Journals (Sweden)

La Harimu

2010-06-01

Full Text Available Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II  metal ions had been separated using poly(eugenyl oxyacetic acid as an ion carrier by bulk liquid membrane transport method. The effect of pH, polyeugenyl oxyacetic acid ion carrier concentration, nitric acid concentration in the stripping solution, transport time, and metal concentration were optimized. The result showed that the optimum condition for transport of metal ions was at pH 4 for ion Fe(III and at pH 5 for Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions. The carrier volumes were optimum with concentration of 1 x 10-3 M at 7.5 mL for Cr(III, Cu (II,  Ni(II, Co(II ions and at 8.5 mL for Fe(III and Pb(II ions. The concentration of HNO3 in stripping phase was optimum at 2 M for Fe(III and Cu(II ions, 1 M for Cr(III, Ni(II and Co(II ions, and 0.5 M for Pb(II ion. The optimum transport times were 36 h for Fe(III and Co(II ions, and 48 h for Cr(III, Cu (II, Ni(II, and Pb(II ions. The concentration of metal ions accurately transported were 2.5 x 10-4 M for Fe(III and Cr(III ions, and 1 M for Cu (II, Ni(II, Co(II, and Pb(II ions. Compared to other metal ions the transport of Fe(III was the highest with selectivity order of Fe(III > Cr(III > Pb(II > Cu(II > Ni(II > Co(II. At optimum condition, Fe(III ion was transported through the membrane at 46.46%.   Keywords: poly(eugenyl oxyacetic acid, transport, liquid membrane, Fe (III, Cr(III, Cu(II, Ni(II, Co(II, and Pb(II ions

Investigations on synthesis, coordination behaviour and actinide recovery of unexplored phosphine oxides

International Nuclear Information System (INIS)

Veerashekhar Goud, E.; Pavankumar, B.B.; Das, Dhrubajyothi

2016-01-01

The search for the development of an optimum extractant for effective separation of a particular metal from a mixture is an active field of research in both chemistry and chemical engineering. These extractants find extensive application in extractive metallurgy and in nuclear fuel cycle (for the separation of actinides from other fission products). In the case of the latter, solvent extraction and ion exchange are two widely employed separation techniques. In this connection, the present paper reports synthesis and structural characterization of various new phosphine oxide derivatives. The coordination behavior of these ligands is studied with some selected lanthanides and actinides shows the proposed structures of La(III) and Th(IV) metal complexes. The purity and structural characterization of the ligands and their corresponding metal complexes are analyzed by various analytical and spectroscopic techniques. Additionally, we have applied Density functional theory (DFT) calculations to understand the electronic structure of some metal complexes formed during the extraction process. (author)

Siderocalin-mediated recognition, sensitization, and cellular uptake of actinides.

Science.gov (United States)

Allred, Benjamin E; Rupert, Peter B; Gauny, Stacey S; An, Dahlia D; Ralston, Corie Y; Sturzbecher-Hoehne, Manuel; Strong, Roland K; Abergel, Rebecca J

2015-08-18

Synthetic radionuclides, such as the transuranic actinides plutonium, americium, and curium, present severe health threats as contaminants, and understanding the scope of the biochemical interactions involved in actinide transport is instrumental in managing human contamination. Here we show that siderocalin, a mammalian siderophore-binding protein from the lipocalin family, specifically binds lanthanide and actinide complexes through molecular recognition of the ligands chelating the metal ions. Using crystallography, we structurally characterized the resulting siderocalin-transuranic actinide complexes, providing unprecedented insights into the biological coordination of heavy radioelements. In controlled in vitro assays, we found that intracellular plutonium uptake can occur through siderocalin-mediated endocytosis. We also demonstrated that siderocalin can act as a synergistic antenna to sensitize the luminescence of trivalent lanthanide and actinide ions in ternary protein-ligand complexes, dramatically increasing the brightness and efficiency of intramolecular energy transfer processes that give rise to metal luminescence. Our results identify siderocalin as a potential player in the biological trafficking of f elements, but through a secondary ligand-based metal sequestration mechanism. Beyond elucidating contamination pathways, this work is a starting point for the design of two-stage biomimetic platforms for photoluminescence, separation, and transport applications.

Robust membrane systems for actinide separations

International Nuclear Information System (INIS)

Jarvinen, Gordon D.; McCleskey, T. Mark; Bluhm, Elizabeth A.; Abney, Kent D.; Ehler, Deborah S.; Bauer, Eve; Le, Quyen T.; Young, Jennifer S.; Ford, Doris K.; Pesiri, David R.; Dye, Robert C.; Robison, Thomas W.; Jorgensen, Betty S.; Redondo, Antonio; Pratt, Lawrence R.; Rempe, Susan L.

2000-01-01

Our objective in this project is to develop very stable thin membrane structures containing ionic recognition sites that facilitate the selective transport of target metal ions, especially the actinides

Actinides(3)/lanthanides(3) separation by nano-filtration assisted by complexation; Separation actinides(3)lanthanides(3) par nanofiltration assistee par complexation

Energy Technology Data Exchange (ETDEWEB)

Sorin, A

2006-07-01

In France, one of the research trend concerning the reprocessing of spent nuclear fuel consists to separate selectively the very radio-toxic elements with a long life to be recycled (Pu) or transmuted (Am, Cm, Np). The aim of this thesis concerns the last theme about actinides(III)/lanthanides(III) separation by a process of nano-filtration assisted by complexation. Thus, a pilot of tangential membrane filtration was designed and established in a glove box at the ATALANTE place of CEA-Marcoule. Physico-chemical characterisation of the Desal GH membrane (OSMONICS), selected to carry out actinides(III)/lanthanides(III) separation, was realized to determine the zeta potential of the active layer and its resistance to ionizing radiations. Moreover, a parametric study was also carried out to optimize the selectivity of complexation, and the operating conditions of complex retention (influences of the transmembrane pressure, solute concentration, tangential velocity and temperature). Finally, the separation of traces of Am(III) contained in a mixture of lanthanides(III), simulating the real load coming from a reprocessing cycle, was evaluated with several chelating agents such as poly-amino-carboxylic acids according to the solution acidity and the [Ligand]/[Cation(III)] ratio. (author)

Factors influencing the transport of actinides in the groundwater environment. Final report

International Nuclear Information System (INIS)

Sheppard, J.C.; Kittrick, J.A.

1983-01-01

This report summarizes investigations of factors that significantly influence the transport of actinide cations in the groundwater environment. Briefly, measurements of diffusion coefficients for Am(III), Cm(III), and Np(V) in moist US soils indicated that diffusion is negligible compared to mass transport in flowing groundwater. Diffusion coefficients do, however, indicate that, in the absence of flowing water, actinide elements will migrate only a few centimeters in a thousand years. The remaining investigations were devoted to the determination of distribution ratios (K/sub d/s) for representative US soils, factors influencing them, and chemical and physical processes related to transport of actinides in groundwaters. The computer code GARD was modified to include complex formation to test the importance of humic acid complexing on the rate of transport of actinides in groundwaters. Use of the formation constant and a range of humic acid, even at rather low concentrations of 10 -5 to 10 -6 molar, significantly increases the actinide transport rate in a flowing aquifer. These computer calculations show that any strong complexing agent will have a similar effect on actinide transport in the groundwater environment. 32 references, 9 figures

Developing laser ablation in an electron cyclotron resonance ion source for actinide detection with AMS

Energy Technology Data Exchange (ETDEWEB)

Bauder, W. [Argonne National Laboratory, Physics Division, 9600 S. Cass Ave, Lemont, IL 60439 (United States); University of Notre Dame, Nuclear Science Laboratory, 124 Nieuwland Science Hall, Notre Dame, IN 46556 (United States); Pardo, R.C.; Kondev, F.G.; Kondrashev, S.; Nair, C.; Nusair, O. [Argonne National Laboratory, Physics Division, 9600 S. Cass Ave, Lemont, IL 60439 (United States); Palchan, T. [Hebrew University, Racah Institute of Physics, Jerusalem 91904 (Israel); Scott, R.; Seweryniak, D.; Vondrasek, R. [Argonne National Laboratory, Physics Division, 9600 S. Cass Ave, Lemont, IL 60439 (United States); Collon, P. [University of Notre Dame, Nuclear Science Laboratory, 124 Nieuwland Science Hall, Notre Dame, IN 46556 (United States); Paul, M. [Hebrew University, Racah Institute of Physics, Jerusalem 91904 (Israel)

2015-10-15

A laser ablation material injection system has been developed at the ATLAS electron cyclotron resonance (ECR) ion source for use in accelerator mass spectrometry experiments. Beam production with laser ablation initially suffered from instabilities due to fluctuations in laser energy and cratering on the sample surface by the laser. However, these instabilities were rectified by applying feedback correction for the laser energy and rastering the laser across the sample surface. An initial experiment successfully produced and accelerated low intensity actinide beams with up to 1000 counts per second. With continued development, laser ablation shows promise as an alternative material injection scheme for ECR ion sources and may help substantially reduce cross talk in the source.

Structural organization and spectroscopy of peptide-actinide(IV) complexes

International Nuclear Information System (INIS)

Dahou, S.

2010-01-01

The contamination of living organisms by actinide elements is at the origin of both radiological and chemical toxicity that may lead to severe dysfunction. Most of the data available on the actinide interaction with biological systems are macroscopic physiological measurements and are lacking a molecular description of the systems. Because of the intricacy of these systems, classical biochemical methods are difficult to implement. Our strategy consisted in designing simplified biomimetic peptides, and describing the corresponding intramolecular interactions with actinides. A carboxylic pentapeptide of the form DDPDD has been at the starting point of this work in order to further assess the influence of the peptide sequence on the topology of the complexes.To do so, various linear (Asp/Ala permutations, peptoids) and cyclic analogues have been synthesized. Furthermore, in order to include the hydroxamic function (with a high affinity for Fe(III)) in the peptide, both desferrioxamine and acetohydroxamic acid have been investigated. However because of difficulties in synthesis, we have not been able to test these peptides. Three actinide cations have been considered at oxidation state +IV (Th, Np, Pu) and compared to Fe(III), often considered as a biological surrogate of Pu(IV). The spatial arrangement of the peptide around the cation has been probed by spectrophotometry and X-ray Absorption Spectroscopy. The spectroscopic data and EXAFS data adjustment lead us to rationalize the topology of the complexes as a function of the peptide sequence: mix hydroxy polynuclear species for linear and cyclic peptides, mononuclear for the desferrioxamine complexes. Furthermore, significant differences have appeared between Fe(III) and actinide(IV), related to differences of reactivity in aqueous medium. (author)

Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry

International Nuclear Information System (INIS)

Vercouter, Th.

2005-03-01

The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO 3 ) 3 3- , is identified by solubility measurements in Na 2 CO 3 solutions. Then the formation constants of the complexes Eu(CO 3 ) i 3-2i (i=1-3) and Eu(SO 4 ) i 3-2i (i=1-2) are measured by TRLFS. The formation of aqueous LaSO 4 + is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO 3 ) 2 - + CO 3 2- ↔ Cm(CO 3 ) 3 3- are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

Thermodynamic approach of the poly-azine - f element ions interaction in aqueous conditions

International Nuclear Information System (INIS)

Miguirditchian, M.; Guillaumont, D.; Moisy, P.; Guillaneux, D.; Madic, C.

2004-01-01

2-Amino-4,6-di-(pyridine-2-yl)-1,3,5-triazine (Adptz) was considered as a model compound for selective aromatic nitrogen extractants (poly-azines) of minor actinides. Thermodynamic data ( ΔG 0 , ΔH 0 , ΔS 0 ) were systematically acquired for the complexation of lanthanide(III) ions as well as yttrium(III) and americium(III) in hydro-alcoholic medium. Two complementary experimental approaches were followed. Stability constants for the formation of the 1:1 complexes were evaluated from UV-visible spectrophotometry titration experiments, whereas enthalpies and entropies of reaction were obtained consistently from either temperature dependence experiments or micro-calorimetry. The interaction of Adptz with lanthanide(III) and yttrium(III) ions was found to be essentially ionic and dependent upon the hydration and size of the ion. As for americium(III) ion, stability constant and enthalpy of complexation was significantly larger. This was attributed to a partial electronic transfer from the ligand to empty orbitals of the cation. DFT calculations support this interpretation. (authors)

Self-interaction corrected local spin density calculations of actinides

DEFF Research Database (Denmark)

Petit, Leon; Svane, Axel; Szotek, Z

2010-01-01

We use the self-interaction corrected local spin-density approximation in order to describe localization-delocalization phenomena in the strongly correlated actinide materials. Based on total energy considerations, the methodology enables us to predict the ground-state valency configuration...... of the actinide ions in these compounds from first principles. Here we review a number of applications, ranging from electronic structure calculations of actinide metals, nitrides and carbides to the behaviour under pressure of intermetallics, and O vacancies in PuO2....

Highly efficient separation materials created by computational approach. For the separation of lanthanides and actinides

International Nuclear Information System (INIS)

Goto, Masahiro; Uezu, Kazuya; Aoshima, Atsushi; Koma, Yoshikazu

2002-05-01

In this study, efficient separation materials have been created by the computational approach. Based on the computational calculation, novel organophosphorus extractants, which have two functional moieties in the molecular structure, were developed for the recycle system of transuranium elements using liquid-liquid extraction. Furthermore, molecularly imprinted resins were prepared by the surface-imprint polymerization technique. Thorough this research project, we obtained two principal results: 1) design of novel extractants by computational approach, and 2) preparation of highly selective resins by the molecular imprinting technique. The synthesized extractants showed extremely high extractability to rare earth metals compared to those of commercially available extractants. The results of extraction equilibrium suggested that the structural effect of extractants is one of the key factors to enhance the selectivity and extractability in rare earth extractions. Furthermore, a computational analysis was carried out to evaluate the extraction properties for the extraction of rare earth metals by the synthesized extractants. The computer simulation was shown to be very useful for designing new extractants. The new concept to connect some functional moieties with a spacer is very useful and is a promising method to develop novel extractants for the treatment of nuclear fuel. In the second part, we proposed a novel molecular imprinting technique (surface template polymerization) for the separation of lanthanides and actinides. A surface-templated resin is prepared by an emulsion polymerization using an ion-binding (host) monomer, a resin matrix-forming monomer and the target Nd(III) metal ion. A host monomer which has amphiphilic nature forms a complex with a metal ion at the interface, and the complex remains as it is. After the matrix is polymerized, the coordination structure is 'imprinted' at the resin interface. Adsorption of Nd(III) and La(III) ions onto the

Electrorecovery of actinides at room temperature

Energy Technology Data Exchange (ETDEWEB)

Stoll, Michael E [Los Alamos National Laboratory; Oldham, Warren J [Los Alamos National Laboratory; Costa, David A [Los Alamos National Laboratory

2008-01-01

There are a large number of purification and processing operations involving actinide species that rely on high-temperature molten salts as the solvent medium. One such application is the electrorefining of impure actinide metals to provide high purity material for subsequent applications. There are some drawbacks to the electrodeposition of actinides in molten salts including relatively low yields, lack of accurate potential control, maintaining efficiency in a highly corrosive environment, and failed runs. With these issues in mind we have been investigating the electrodeposition of actinide metals, mainly uranium, from room temperature ionic liquids (RTILs) and relatively high-boiling organic solvents. The RTILs we have focused on are comprised of 1,3-dialkylimidazolium or quaternary ammonium cations and mainly the {sup -}N(SO{sub 2}CF{sub 3}){sub 2} anion [bis(trif1uoromethylsulfonyl)imide {equivalent_to} {sup -}NTf{sub 2}]. These materials represent a class of solvents that possess great potential for use in applications employing electrochemical procedures. In order to ascertain the feasibility of using RTILs for bulk electrodeposition of actinide metals our research team has been exploring the electron transfer behavior of simple coordination complexes of uranium dissolved in the RTIL solutions. More recently we have begun some fundamental electrochemical studies on the behavior of uranium and plutonium complexes in the organic solvents N-methylpyrrolidone (NMP) and dimethylsulfoxide (DMSO). Our most recent results concerning electrodeposition will be presented in this account. The electrochemical behavior of U(IV) and U(III) species in RTILs and the relatively low vapor pressure solvents NMP and DMSO is described. These studies have been ongoing in our laboratory to uncover conditions that will lead to the successful bulk electrodeposition of actinide metals at a working electrode surface at room temperature or slightly elevated temperatures. The RTILs we

Selective extraction of actinides from high level liquid wastes. Study of the possibilities offered by the Redox properties of actinides

International Nuclear Information System (INIS)

Adnet, J.M.

1991-07-01

Partitioning of high level liquid wastes coming from nuclear fuel reprocessing by the PUREX process, consists in the elimination of minor actinides (Np, Am, and traces of Pu and U). Among the possible processes, the selective extraction of actinides with oxidation states higher than three is studied. First part of this work deals with a preliminary step; the elimination of the ruthenium from fission products solutions using the electrovolatilization of the RuO4 compound. The second part of this work concerns the complexation and oxidation reactions of the elements U, Np, Pu and Am in presence of a compound belonging to the insaturated polyanions family: the potassium phosphotungstate. For actinide ions with oxidation state (IV) complexed with phosphotungstate anion the extraction mechanism by dioctylamine was studied and the use of a chromatographic extraction technic permitted successful separations between tetravalents actinides and trivalents actinides. Finally, in accordance with the obtained results, the basis of a separation scheme for the management of fission products solutions is proposed

Separation of lanthanides (III) and actinides (III) by calixarenes containing acetamide-phosphine oxides functions

International Nuclear Information System (INIS)

Garcia Carrera, A.; Dozol, J.F.; Rouquette, H.

2001-01-01

The carbamoyl methyl phosphine oxide CMPO is the well known extractant of the TRUEX process for extraction of actinides from highly salted acidic wastes. In the framework of an European research contract coordinated by CEA/DDCC. V. Boehmer (Mainz, Germany) synthesized calix(4)arenes bearing CMPO moieties either on the wide rim, or on the narrow rim. Some of these calixarenes used at a concentration 10 -3 M are more efficient than CMPO used at a two hundred fifty fold higher concentration. Moreover, calixarene skeleton leads to a strong selectivity among lanthanides, this selectivity is much less obvious for CMPO. Selectivity order is reversed according to whether CMPO unit is borne by the wide rim or the narrow rim. The most efficient calixarenes allow actinides to be separated from most of the lanthanides except the lightest ones. (authors)

Liquid–liquid extraction of Pu(IV), U(VI) and Am(III) using malonamide in room temperature ionic liquid as diluent

International Nuclear Information System (INIS)

Rout, Alok; Venkatesan, K.A.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2012-01-01

Highlights: ► Extraction of actinides using malonamide in room temperature ionic liquid. ► High distribution ratios of actinides in room temperature ionic liquid. ► Ion exchange mechanism. ► Stoichiometry of extraction. ► High separation factors of U(VI) and Pu(IV) over Am(III) and fission products. - Abstract: The extraction behavior of U(VI), Pu(IV) and Am(III) from nitric acid medium by a solution of N,N-dimethyl-N,N-dioctyl-2-(2-hexyloxyethyl)malonamide (DMDOHEMA) in the room temperature ionic liquid, 1–butyl–3–methylimidazolium bis(trifluoromethanesulfonyl)imide (C 4 mimNTf 2 ), was studied. The distribution ratio of these actinides in DMDOHEMA/C 4 mimNTf 2 was measured as a function of various parameters such as the concentration of nitric acid, DMDOHEMA, NTf 2 − , alkyl chain length of ionic liquid. The extraction of actinides in the absence of DMDOHEMA was insignificant and the distribution ratio achieved in conjunction with C 4 mimNTf 2 , was remarkable. The separation factor of U(VI) and Pu(IV) achieved with the use of DMDOHEMA, ionic liquid was compared with Am(III) and other fission products. The stoichiometry of the metal-solvate was determined to be 1:2 for U(VI) and Pu(IV) and 1:3 for Am(III).

Trivalent lanthanide/actinide separation in the spent nuclear fuel wastes' reprocessing

International Nuclear Information System (INIS)

Narbutt, J.; Krejzler, J.

2006-01-01

Separation of trivalent actinides, in particular americium and curium, from lanthanides is an important step in an advanced partitioning process for future reprocessing of spent nuclear fuels. Since the trivalent actinides and lanthanides have similar chemistries, it is rather difficult to separate them from each other. The aim of presented work was to study solvent extraction of Am(III) and Eu(III) in a system containing diethylhemi-BTP (6-(5,6-diethyl-1,2,4-triazin-3-yl)-2,2'-bipyridine) and COSAN (protonated bis(chlorodicarbollido)cobalt(III)). The system was chosen by several groups working in the integrated EC research Project EUROPART. Several physicochemical properties of the extraction system were analyzed and discussed

Effects of humic substances on the migration of radionuclides: Complexation of actinides with humic substances. 1. progress report

International Nuclear Information System (INIS)

Kim, J.I.; Buckau, G.; Klenze, R.; Rhee, D.S.; Wimmer, H.; Decambox, P.; Mauchien, P.; Moulin, C.; Moulin, V.; Tits, J.; Marquardt, C.; Riegel, J.; Sattelberger, P.; Herrmann, G.; Trautmann, N.; Diercks, A.; Vancluysen, J.; Maes, A.; Bidoglio, G.; Righetto, L.

1992-02-01

The aim of the present research programme is to study the complexation behaviour of actinide ions with humic substances in natural aquifer systems and hence to quantify the effect of humic substances on the actinide migration. Aquatic humic substances commonly found in all groundwaters in different concentrations have a strong tendency towards complexation with actinide ions. This is one of the major geochemical reactions but hitherto least quantified. Therefore, the effect of humic substances on the actinide migration is poorly understood. In the present research programme the complexation of actinide ions with humic substances will be described thermodynamically. This description will be based on a model being as simple as possible to allow an easy introduction of the resulting constants into geochemical modelling of the actinide migration. This programme is a continuation of the activities of the COCO group in the second phase of the CEC-MIRAGE project. (orig.)

A spectroscopic screening of the chemical speciation of europium(III) in gastrointestinal tract. The intestine

Energy Technology Data Exchange (ETDEWEB)

Wilke, Claudia; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements

2016-07-01

To evaluate the health risks of lanthanides (Ln) and radiotoxic actinides (An), investigations into the chemical reactions of these metals in the human gastrointestinal tract are necessary. In order to identify the dominant binding partners (i.e. counter ions and/or ligands) of An/Ln in the gastrointestinal tract, a spectroscopic screening was performed by Time-Resolved Laser-induced Fluorescence Spectroscopy (TRLFS) using artificial digestive juices containing Eu(III), a representative of Ln(III) and An(III). In the intestine, Eu(III) show a strong complexation especially with organic substances of the pancreatic and bile juice like the protein mucin.

Luminescence study on solvation of americium(III), curium(III) and several lanthanide(III) ions in nonaqueous and binary mixed solvents

International Nuclear Information System (INIS)

Kimura, T.; Nagaishi, R.; Kato, Y.; Yoshida, Z.

2001-01-01

The luminescence lifetimes of An(III) and Ln(III) ions [An=Am and Cm; Ln=Nd, Sm, Eu, Tb and Dy] were measured in dimethyl sulfoxide(DMSO), N,N-dimethylformamide(DMF), methanol(MeOH), water and their perdeuterated solvents. Nonradiative decay rates of the ions were in the order of H 2 O > MeOH > DMF > DMSO, indicating that O-H vibration is more effective quencher than C-H, C=O, and S=O vibrations in the solvent molecules. Maximal lifetime ratios τ D /τ H were observed for Eu(III) in H 2 O, for Sm(III) in MeOH and DMF, and for Sm(III) and Dy(III) in DMSO. The solvent composition in the first coordination sphere of Cm(III) and Ln(III) in binary mixed solvents was also studied by measuring the luminescence lifetime. Cm(III) and Ln(III) were preferentially solvated by DMSO in DMSO-H 2 O, by DMF in DMF-H 2 O, and by H 2 O in MeOH-H 2 O over the whole range of the solvent composition. The order of the preferential solvation, i.e., DMSO > DMF > H 2 O > MeOH, correlates with the relative basicity of these solvents. The Gibbs free energy of transfer of ions from water to nonaqueous solvents was further estimated from the degree of the preferential solvation. (orig.)

Spectroscopic and thermodynamic study of the complexation of Cm(III) and Eu(III) with hydrophilic bis-triazinyl pyridines

International Nuclear Information System (INIS)

Ruff, Christian

2013-01-01

In the present work the complexation of Cm(III) and Eu(III) with a hydrophilic 2,6-bis-(1,2,4-triazinyl)-pyridine (aq-BTP) is studied. Aq-BTP complexes actinides(III) selectively over lanthanides(III) in nitric acid solution. The object of this work is the identification and the spectroscopic and thermodynamic characterization of the Cm(III) and Eu(III) complex species present in solution. The results should contribute to a better fundamental understanding of the driving force behind BTPs selectivity towards trivalent actinides on a molecular level. Time-resolved laser fluorescence spectroscopy (TRLFS), luminescence and UV/Vis spectroscopy are applied. Information on the structure of M(III)-aq-BTP complex species is obtained from density functional theory. Three different M(III) complex species containing one, two or three aq-BTP ligands are identified in H 2 O at pH 3.0. Relative fluorescence intensity factors are determined for each of the [M(aq-BTP) n ] complexes (M = Cm(III)/Eu(III), n = 1 - 3). These factors are required to quantify the complexes. The stability constant logβ 3 of the [Cm(aq-BTP) 3 ] complex (which is the one relevant to extraction processes) is two orders of magnitude higher than that of the corresponding Eu(III) complex. This difference is in agreement with the separation factor (SF Am(III)/Eu(III) = 150) determined experimentally by liquid-liquid extraction. The difference in the stability constants originates from the different reaction enthalpies for the formation of the [M(aq-BTP) 3 ] complexes. These results represent the thermodynamic driving force for the aq-BTPs selectivity towards trivalent actinides over lanthanides. Comparing the stability constants of the [M(aq-BTP) n ] species (M = Cm(III)/Eu(III), n = 1 - 3) shows an increasing selectivity with increasing number of coordinated aq-BTP ligands. Hence, high selectivity is achieved if the f-element ions are fully coordinated by nine N-donor atoms (three aq-BTP ligands). A less

Complexation of Eu(III) with a polymeric cement additive as a potential carrier of actinides

Energy Technology Data Exchange (ETDEWEB)

Lippold, Holger; Becker, Michael [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Reactive Transport

2017-06-01

In the long term, cementitious materials in a final repository will be exposed to leaching processes generating highly alkaline solutions. Polymeric additives, so-called superplasticizers, are considered as potential mobilizing agents for released radionuclides, since it is uncertain whether complete degradation will take place under the evolving aqueous conditions. Regarding the complexing properties of superplasticizers, there are only indirect assessments so far. In this study, first systematic investigations on complexation with Eu(III) as an analogue of trivalent actinides were performed at variable pH and electrolyte content (NaCl, CaCl{sub 2}) using ultrafiltration as a separation method. A stability constant was derived according to the charge neutralization model. For this purpose, the proton exchange capacity was determined by potentiometric titration.

Effects of humic substances on the migration of radionuclides: Complexation of actinides with humic substances. 3. Progress report

International Nuclear Information System (INIS)

Kim, J.I.; Rhee, D.S.; Buckau, G.; Moulin, V.; Tits, J.; Decambox, P.; Franz, C.; Herrmann, G.; Trautmann, N.; Dierckx, A.; Vancluysen, J.; Maes, A.

1993-03-01

The aim of the present research programme is to study the complexation behaviour of actinide ions with humic substances in natural aquifer systems and hence to quantify the effect of humic substances on the actinide migration. Aquatic humic substances commonly found in all groundwaters in different concentrations have a strong tendency towards complexation with actinide ions. This is one of the major geochemical reactions but hitherto least quantified. Therefore, the effect of humic substances on the actinide migration is poorly understood. In the present research programme the complexation of actinide ions with humic substances will be described thermodynamically. This description will be based on a model being as simple as possible to allow an easy introduction of the resulting reaction constants into geochemical modelling of the actinide migration. This programme is a continuation of the activities of the COCO group in the second phase of the CEC-MIRAGE project. The programme consists of the following three main tasks: Task 1: Complexation reactions of actinide ions with well characterized reference and site-specific humic and fulvic acids; Task 2: Competition reactions with major cations in natural groundwaters; Task 3: Validation of the complexation data in natural aquatic systems by comparison of calculation with spectroscopic experiment. (orig./EF)

Evaluation of a novel task specific ionic liquid for actinide ion extraction

International Nuclear Information System (INIS)

Paramanik, M.; Ghosh, S.K.; Raut, D.R.; Mohapatra, P.K.

2016-01-01

Separation of U and Pu from nuclear waste is of great relevance for a sustainable closed fuel cycle point of view. Spent fuel reprocessing by the well known PUREX process is done world wide for the recovery of U and Pu using TBP as the extractant. Room temperature ionic liquids (RTILs) have shown significantly higher extraction of metal ions, particularly at lower acidity as compared to the molecular diluents. Functionalization of ionic liquids has resulted in highly efficient task specific ionic liquids (TSILs) with superior extraction properties than the analogous extractants dissolved in ionic liquids. The present paper reports the evaluation of a novel task specific ionic liquid (TSIL) containing >P=O functional group for the extraction of actinides like U(VI) and Pu(IV)

Static and dynamic modelling of lanthanide and actinide cations in solution

International Nuclear Information System (INIS)

Marjolin, A.

2012-01-01

We propose a theoretical approach, based on both quantum analyses (energy decomposition analysis and topological analysis of the chemical bond) and classical molecular dynamics, for the study of f-element complexes. First, we introduce the different QM methods adapted to the study of f-elements and use them for geometry optimization and interaction energy calculations of the model system [M-(OH 2 )] m+ where M is a lanthanide or actinide cation. We then perform energy decomposition analysis to quantify the physical nature of the metal-ligand interaction in terms of the different contributions. Furthermore, the different energy contributions will be used as reference curves for the parameterization of the polarizable force fields AMOEBA and SIBFA. Next, starting from the optimized geometries, we establish the reference diabatic dissociation curves at high level of theory so as to take into account the multi-reference nature of the systems. These dissociation curves will also be used for parameterization of the AMOEBA potential. We then propose a three step validation protocol as well as a first application, it being the computation of Gibbs hydration free energies for the f-element cations. We also propose an extension of the SIBFA force field to trivalent lanthanide ions and tetravalent actinide ions. Last, we use the topological analysis approaches of ELF and NCI to investigate the nature of the different interactions in Gadolinium(III) model and real systems. The aim of the whole study was to develop and apply different theoretical approaches so as to be able to discriminate between lanthanide and actinide cations. Indeed, despite their similar chemical behavior, they still feature a selective character that we wish to be able to both explain and predict. (author) [fr

Determination of actinides using ICP-SFMS

International Nuclear Information System (INIS)

Nygren, Ulrika

2006-01-01

Interest in the determination of the actinides using ICP-MS has steadily increased with the development of systems capable of more sensitive and precise measurements. However, the analysis of less abundant actinides such as Pu and Am is not straightforward due to the need for chemical separation of these elements prior to determination. In many applications of mass-spectrometric actinide analysis, isotope ratio measurements are important, either for the analysis of the isotopic composition of, e.g., U or Pu in the sample, or for quantitative determinations using isotope dilution mass spectrometry. In order to achieve high precision and accuracy in an isotope ratio measurement, corrections for instrumentally induced systematic errors, e.g., due to dead-time and mass bias, need to be considered. In this thesis, different aspects of actinide analysis using ICP-SFMS have been addressed. In Papers I and III, separation procedures based on solid phase extraction for Pu, Am and U were developed and evaluated with respect to chemical yield and separation from elements causing spectral interferences. Applications of the analytical procedures developed comprised measurement of the 240 Pu/ 2 3 9Pu ratio in environmental reference materials, and age determination of Pu based on the 241 Pu/ 241 Am and 240 Pu/ 236 U ratios. In the application of different separation procedures for Pu, previously unidentified spectral interferences were discovered. In Paper II, these interferences were identified as lanthanide phosphate ions and the composition and formation of these species with respect to different instrumental parameters were further examined. Due to the importance of precise and accurate isotope ratio determination, a thorough investigation of the instrumental dead time of an ICP-SFMS system was performed. The dead time was evaluated via both isotope ratio and electronic measurements of the output from the detector amplifier. It was found that the overall uncertainty in ratio

Uranium (III)-Plutonium (III) co-precipitation in molten chloride

Science.gov (United States)

Vigier, Jean-François; Laplace, Annabelle; Renard, Catherine; Miguirditchian, Manuel; Abraham, Francis

2018-02-01

Co-management of the actinides in an integrated closed fuel cycle by a pyrochemical process is studied at the laboratory scale in France in the CEA-ATALANTE facility. In this context the co-precipitation of U(III) and Pu(III) by wet argon sparging in LiCl-CaCl2 (30-70 mol%) molten salt at 705 °C is studied. Pu(III) is prepared in situ in the molten salt by carbochlorination of PuO2 and U(III) is then introduced as UCl3 after chlorine purge by argon to avoid any oxidation of uranium up to U(VI) by Cl2. The oxide conversion yield through wet argon sparging is quantitative. However, the preferential oxidation of U(III) in comparison to Pu(III) is responsible for a successive conversion of the two actinides, giving a mixture of UO2 and PuO2 oxides. Surprisingly, the conversion of sole Pu(III) in the same conditions leads to a mixture of PuO2 and PuOCl, characteristic of a partial oxidation of Pu(III) to Pu(IV). This is in contrast with coconversion of U(III)-Pu(III) mixtures but in agreement with the conversion of Ce(III).

Organometallic neptunium(III) complexes.

Science.gov (United States)

Dutkiewicz, Michał S; Farnaby, Joy H; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G; Love, Jason B; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on U(III) and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to Np(IV). Here we report the synthesis of three new Np(III) organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that Np(III) complexes could act as single-molecule magnets, and that the lower oxidation state of Np(II) is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key Np(III) orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

The role of humic acid on the formation of HAS (hydroxy-aluminosilicate) colloid-borne actinides

Energy Technology Data Exchange (ETDEWEB)

Priemyshev, A.; Kim, M.A. [Inst. fuer Radiochemie, Technische Universitaet Muenchen, D-85748 Garching (Germany); Breban, D.; Panak, P.J.; Yun, J.I.; Kim, J.I.; Fanghanel, Th. [Inst. fuer Nukleare Entsorgung, Forschungszentrum Karlsruhe, D-76021 Karlsruhe (Germany); Mansel, A. [Inst. fuer Interdisziplinaere Isotopenforschung, Georadiochemie, Leipzig, D-04318 Leipzig (Germany)

2005-07-01

Full text of publication follows: One of the major unknowns in the process of actinide migration is the formation of their colloid-borne species. Previous studies have been directed to the incorporation of actinides into HAS (hydroxy-aluminosilicate) colloids generated by the nucleation of Si and Al. The present work further pursues the behaviour of actinides at HAS colloid formation but in the presence of humic acid that is known to be an ubiquitous groundwater constituent. The formation and degree of stability of the aluminosilicate binding for the generation of HAS colloids are investigated at first in the absence of actinides. Free and complexed Al resulting from ligand competitions reactions for the complexation of Al with mono-silicic acid, poly-silicic acid and EDTA are monitored spectroscopically by colour reaction. The second part of the study concentrates on the formation and stability of humic colloids using {sup 14}C-labeled humic acid. The activity distribution is ascertained in the ionic, colloidal and precipitated fractions under different conditions of colloid formation, e.g. as a function of pH, time, humic acid and Al concentration. The third part follows the appraisal of appropriate conditions under which stable HAS and humic colloids are formed, and their interaction with actinides, either separately or in competition. Trace actinides of different oxidation states {sup 241}Am(III), {sup 234}Th(IV) and {sup 233}U(VI) are taken for the purpose. HAS colloids generated from poly-silicic acid at neutral pH show EDTA-resistance, whereas HAS colloids formed from mono-silicic acid become EDTA-resistant only by aging (> one month). Humic acid appears to stabilize HAS colloids, unless the loading capacity of humic acid for the Al ion is exceeded. The incorporation of actinides into the colloidal phase is generally enhanced in the presence of humic acid. Synergic effects produce chimeric HAS-humic colloids into which tri-, tetra- and hexavalent actinides

Interaction of selected actinides (U, Cm) with bacteria relevant to nuclear waste disposal

Energy Technology Data Exchange (ETDEWEB)

Luetke, Laura

2013-07-01

To assess the safety of a site destined for storage of nuclear waste enhanced research effort is demanded to investigate the complex interactions of released radionuclides with parts of the environment that includes indigenous microorganisms. This work aimed at assessing the interactions of two bacterial strains with the actinides uranium and curium with a focus on thermodynamics to provide stability constants of the actinide bacteria species formed usable for modelling the distribution of these actinides in the environment. The influences of Pseudomonas fluorescens (CCUG 32456A) isolated from the granitic aquifers at Aespoe(Sweden) and a novel isolate from Mont Terri Opalinus clay (Switzerland), Paenibacillus sp. MT-2.2, were investigated. A combined approach using microbiological and spectroscopic techniques as well as potentiometry was employed to characterize the U(VI) and Cm(III) binding onto the cell surface functional groups structurally and thermodynamically. Further, due to its similar ionic radius to Cm(III) also Eu(III) was studied as non-radioactive analog.

Recovery of actinides from actinide-aluminium alloys by chlorination: Part III - Chlorination with HCl(g)

Science.gov (United States)

Meier, Roland; Souček, Pavel; Walter, Olaf; Malmbeck, Rikard; Rodrigues, Alcide; Glatz, Jean-Paul; Fanghänel, Thomas

2018-01-01

Two steps of a pyrochemical route for the recovery of actinides from spent metallic nuclear fuel are being investigated at JRC-Karlsruhe. The first step consists in electrorefining the fuel in molten salt medium implying aluminium cathodes. The second step is a chlorination process for the separation of actinides (An) from An-Al alloys formed on the cathodes. The chlorination process, in turn, consists of three steps; the distillation of adhered salt (1), the chlorination of An-Al by HCl/Cl2 under formation of AlCl3 and An chlorides (2), and the subsequent sublimation of AlCl3 (3). In the present work UAl2, UAl3, NpAl2, and PuAl2 were chlorinated with HCl(g) in a temperature range between 300 and 400 °C forming UCl4, NpCl4 or PuCl3 as the major An containing phases, respectively. Thermodynamic calculations were carried out to support the experimental work. The results showed a high chlorination efficiency for all used starting materials and indicated that the sublimation step may not be necessary when using HCl(g).

Supercritical fluid carbon dioxide extraction of actinides

International Nuclear Information System (INIS)

Rao, Ankita; Tomar, B.S.

2016-01-01

Supercritical fluid extraction (SFE) is a process akin to liquid-liquid or solvent extraction where a Supercritical fluid (SCF) is contacted with a solid/ liquid matrix for the purpose of separating the component of interest from the original matrix. Carbon dioxide is a preferred choice as supercritical fluid (SCF) owing to its moderate critical parameter (P c = 7.38 MPa and T c = 304.1K) coupled with radiation and chemical stability, non toxic nature and low cost. Despite widespread applications for extraction of organic compounds and associated advantages especially liquid waste minimization, the SFE of metal ions was left unexplored for quite some time, as direct metal ion extraction is inefficient due charge neutralization requirement and weak solute-solvent interaction. Neutral SCF soluble metal-ligand complexation is imperative and SFE of actinides was reported only in 1994. Several studies have been carried out on SFE of uranium, thorium and plutonium from nitric acid medium employing different sets of ligands (organophosphorus, diketones, amides). Especially attractive is the possibility of direct dissolution and extraction of actinides employing ligand-acid adducts (like TBP.HNO 3 adduct) from solid matrices of different stages of nuclear fuel cycle viz. ores, spent nuclear fuels and radioactive wastes. Also, partitioning of actinides from fission products has been explored in spent nuclear fuel. These studies on supercritical fluid extraction of actinides indicate a more efficient and environmentally sustainable technology. (author)

Characterization of partitioning relevant lanthanide and actinide complexes by NMR spectroscopy; Charakterisierung von partitioningrelevanten Lanthaniden- und Actinidenkomplexen mittels NMR-Spektroskopie

Energy Technology Data Exchange (ETDEWEB)

Adam, Christian

2016-01-15

In the present work the interaction of N-donor ligands, such as 2,6-Bis(5,6-dipropyl-1,2,4-triazin-3-yl)pyridine (nPrBTP) and 2,6-Bis(5-(2,2-dimethylpropyl)1H-pyrazol)-3-yl-pyridine (C5-BPP), with trivalent lanthanide and actinide ions was studied. Ligands of this type show a high selectivity for the separation of trivalent actinide ions over lanthanides from nitric acid solutions. However, the reason for this selectivity, which is crucial for future partitioning and transmutation strategies for radioactive wastes, is still unknown. So far, the selectivity of some N-donor ligands is supposed to be an effect of an increased covalency in the actinide-ligand bond, compared to the lanthanide compounds. NMR spectroscopy on paramagnetic metal complexes is an excellent tool for the elucidation of bonding modes. The overall paramagnetic chemical shift consists of two contributions, the Fermi Contact Shift (FCS), due to electron spin delocalisation through covalent bonds, and the Pseudo Contact Shift (PCS), which describes the dipolar coupling of the electron magnetic moment and the nuclear spin. By assessing the FCS share in the paramagnetic shift, the degree of covalency in the metal-ligand bond can be gauged. Several methods to discriminate FCS and PCS have been used on the data of the nPrBTP- and C5-BPP-complexes and were evaluated regarding their applicability on lanthanide and actinide complexes with N-donor ligands. The study comprised the synthesis of all Ln(III) complexes with the exceptions of Pm(III) and Gd(III) as well as the Am(III) complex as a representative of the actinide series with both ligands. All complexes were fully characterised ({sup 1}H, {sup 13}C and {sup 15}N spectra) using NMR spectroscopy. By isotope enrichment with the NMR-active {sup 15}N in positions 8 and 9 in both ligands, resonance signals of these nitrogen atoms were detected for all complexes. The Bleaneymethod relies on different temperature dependencies for FCS (T{sup -1}) and PCS (T

Minor actinide transmutation using minor actinide burner reactors

International Nuclear Information System (INIS)

Mukaiyama, T.; Yoshida, H.; Gunji, Y.

1991-01-01

The concept of minor actinide burner reactor is proposed as an efficient way to transmute long-lived minor actinides in order to ease the burden of high-level radioactive waste disposal problem. Conceptual design study of minor actinide burner reactors was performed to obtain a reactor model with very hard neutron spectrum and very high neutron flux in which minor actinides can be fissioned efficiently. Two models of burner reactors were obtained, one with metal fuel core and the other with particle fuel core. Minor actinide transmutation by the actinide burner reactors is compared with that by power reactors from both the reactor physics and fuel cycle facilities view point. (author)

Actinides and rare earths complexation with adenosine phosphate nucleotides

International Nuclear Information System (INIS)

Mostapha, Sarah

2013-01-01

demonstrated that the dominant interaction is between the cations and the phosphate groups of the ligands. Complexes with monophosphate ligands (AMP-Lu, Lu-Th-AEP and AMP) show similar organizations with bridging phosphates indicating that the organic part does not have a significant effect on their structure. ADP and ATP solid state complexes (with two spheroid metal ions: Lu and Th) show several similarities in terms of local environment indicating that the occurrence of a third phosphate group has no significant effect on the local organization of the complex. However, despite the theoretical approaches that have been conducted, the right structure of these complexes has not been accurately determined. Complexes of lanthanides and actinide(III) (Am) with ATP behave similarly at macroscopic level suggesting an identical structure at the molecular level for these complexes. With uranyl, U-AMP complex synthesized at acidic pH show different behaviour at molecular level than that observed at alkaline pH but the same coordination sites (phosphates and hydroxyls ribose groups) have been demonstrated for both complexes. (author) [fr

Sequential analysis of selected actinides in urine

International Nuclear Information System (INIS)

Kramer, G.H.

1980-07-01

The monitoring of personnel by urinalysis for suspected contamination by actinides necessitated the development and implementation of an analytical scheme that will separate and identify alpha emitting radionuclides of these elements. The present work deals with Pu, Am, and Th. These elements are separated from an ashed urine sample by means of coprecipitation and ion exchange techniques. The final analysis is carried out by electroplating the actinides and counting in a α-spectrometer. Mean recoveries of these elements from urine are: Pu 64%, Am 74% and Th 69%. (auth)

Adsorption Behaviour of La(III and Eu(III Ions from Aqueous Solutions by Hydroxyapatite: Kinetic, Isotherm, and Thermodynamic Studies

Directory of Open Access Journals (Sweden)

F. Granados-Correa

2013-01-01

Full Text Available The hydroxyapatite was successfully synthesized, characterized, and used as an alternative low-cost adsorbent material to study the adsorption behavior of La(III and Eu(III ions from nitrate aqueous solutions as a function of contact time, initial metal ion concentration, pH, and temperature by using a bath technique. The kinetic data correspond very well to the pseudo-second-order equation, and in both cases the uptake was affected by intraparticle diffusion. Isotherm adsorption data were well fitted by the Freundlich model equation with 1/n>1, indicating a multilayer and cooperative-type adsorption. Thermodynamic parameters for the adsorption systems were determinated at 293, 303, 313, and 323 K. These parameters show that adsorptions of La(III and Eu(III ions on hydroxyapatite are endothermic and spontaneous processes. The adsorption was found to follow the order Eu(III > La(III and is dependent on ion concentration, pH, and temperature.

Actinide AMS at DREAMS

Energy Technology Data Exchange (ETDEWEB)

Khojasteh, Nasrin B.; Merchel, Silke; Rugel, Georg; Scharf, Andreas; Ziegenruecker, Rene [HZDR, Dresden (Germany); Pavetich, Stefan [HZDR, Dresden (Germany); ANU, Canberra (Australia)

2016-07-01

Radionuclides such as {sup 236}U and {sup 239}Pu were introduced into the environment by atmospheric nuclear weapon tests, reactor accidents (Chernobyl, Fukushima), releases from nuclear reprocessing facilities (Sellafield, La Hague), radioactive waste disposal, and accidents with nuclear devices (Palomares, Thule) [1]. Accelerator Mass Spectrometry (AMS) is the most sensitive method to measure these actinides. The DREsden AMS (DREAMS) facility is located at a 6 MV accelerator, which is shared with ion beam analytics and implantation users, preventing major modifications of the accelerator and magnetic analyzers. DREAMS was originally designed for {sup 10}Be, {sup 26}Al, {sup 36}Cl, {sup 41}Ca, and {sup 129}I. To modify the system for actinide AMS, a Time-of-Flight (TOF) beamline at the high-energy side has been installed and performance tests are on-going. Ion beam and detector simulations are carried out to design a moveable ionization chamber. Especially, the detector window and anode dimensions have to be optimized. This ionization chamber will act as an energy detector of the system and its installation is planned as closely as possible to the stop detector of the TOF beamline for highest detection efficiency.

Transport behaviour of the lanthanide 152Eu(III), 153Gd(III) and 170Tm(III) and transplutonium element 254Es(III), 244Cm(III), 241Am(III), 249Cf(III) and 249Bk(III) ions in aqueous solutions at 298 K

International Nuclear Information System (INIS)

Ouerfelli, N.

2014-01-01

Ionic self-diffusion coefficients (D) for trivalent radiotracers, lanthanide and actinide ions have been determined in concentrated aqueous solutions of supporting electrolytes of Gd(NO 3 ) 3 -HNO 3 or Nd(ClO 3 ) 4 -HClO 4 up to 1.5 mol L -1 at 298.15 K and pH 2.50 by the open-end capillary method. The data obtained in large range of concentrations, allow to derive the limiting value D deg, the validity of the Onsager limiting law and a more extended law. This study contributes to demonstrate similarities in transport and structure properties between 4f and 5f trivalent ions explained by a similar electronic configuration, ionic radius and hydration number. An empirical equation is suggested for predicting ionic hydration number with a good precision. (author)

Actinide Partitioning and Transmutation Program. Progress report, April 1--June 30, 1977

Energy Technology Data Exchange (ETDEWEB)

Tedder, D. W.; Blomeke, J. O. [comps.

1977-10-01

Experimental work on the 16 tasks comprising the Actinide Partitioning and Transmutation Program was continued. Summaries of work are given on Purex Process modifications, actinide recovery, Am-Cm recovery, radiation effects on ion exchangers, LMFBR transmutation studies, thermal reactor transmutation studies, fuel cycle studies, and partitioning-transmutation evaluation. (JRD)

Research in actinide chemistry. Progress report, March 1, 1980-February 28, 1981

International Nuclear Information System (INIS)

1981-01-01

The primary purpose of this research is to study the behavior of actinide cations in aqueous solution. The interaction of trivalent actinides with a wide variety of both inorganic and organic ligands has been investigated with emphasis on the thermodynamics and kinetics of complexation at tracer concentrations using radiochemical techniques. In order to expand the scope of the experimental techniques, thereby obtaining additional understanding of the fundamental processes involved, non-radioactive experiments with the trivalent lanthanides have been conducted. Visible spectroscopy, nmr ( 1 1 H, 6 13 C, 57 139 La) spectroscopy, potentiometry, solvent extraction and calorimetry are examples of techniques for these lanthanide studies which have allowed much more thorough interpretation of the actinide tracer data due to the close chemical similarity of the lanthanide and actinide families of trivalent cations. The following were investigated: nmr shifts of 139 La for both halate and chloroacetate complexes; interaction of Pu(VI) with carbonates and bicarbonates; Ca +2 , UO 2 +2 , and Th +4 reactions with halate and chloroacetate anions; complexation of the lanthanides by benzoic acid; thermodynamic formation constants for trivalent lanthanide ions with succinic, glutaric, and adipic acids; complexation of benzene polycarboxylates with lanthanides; complexation of lanthanide ions by AMP (adenosine monophosphate), ADP (adenosine diphosphate) and ATP (adenosine triphosphate); interaction of the actinides ions with humic acid; measurements of water and benzoic acid concentrations in several organic solvents by potentiometric and spectral methods; and plutonium and neptunium redox behavior in the presence of organic complexing agents

Effect of iron(III) ion on moso bamboo pyrolysis under microwave irradiation.

Science.gov (United States)

Dong, Qing; Li, Xiangqian; Wang, Zhaoyu; Bi, Yanhong; Yang, Rongling; Zhang, Jinfeng; Luo, Hongzhen; Niu, Miaomiao; Qi, Bo; Lu, Chen

2017-11-01

The effect of iron(III) ion on microwave pyrolysis of moso bamboo was investigated. Hydrofluoric acid washing was used as a pilot process to demineralize moso bamboo in order to eliminate the influences of the other inorganics contained in moso bamboo itself. The results indicated that the addition of iron(III) ion increased the maximal reaction temperatures under microwave condition dependent on the amount of the added iron(III) ion. The production of the non-condensable gases was promoted by the addition of iron(III) ion mainly at the expense of liquid products. Iron(III) ion exhibited the positive effect for syngas production and inhibited the formation of CO 2 and CH 4 . The formation of Fe 2 O 3 and Fe 3 O 4 was found during microwave pyrolysis and the mechanism of the two metallic oxides formation was described in this work. Copyright © 2017 Elsevier Ltd. All rights reserved.

Lanthanides(3)/ actinides (3) separation by nano-filtration-complexation in aqueous medium

International Nuclear Information System (INIS)

Chitry, F.; Pellet-Rostaing, S.; Gozzi, C.; Lemaire, M.; Guy, A.; Foos, J.

2000-01-01

Lanthanides(III)/actinides(III) separation is a major research subject in matter of treatment of high activity liquid effluents. Liquid-liquid extraction actually gives the best results for this separation. In order to demonstrate that nano-filtration (NF) is a valuable alternative to liquid-liquid extraction, we tried to separate different lanthanides(III) with a nano-filtration process combined with a selective complexation step. At first DTPA (diethylene-triamine-pentaacetic acid) combined with a Sepa MG-17 (Osmonics) gave a 95% retention of Gd 3+ and a 50% retention of La 3+ . Then new hydrosoluble and more selective ligands derived from DTPA were synthesized. One of them combined with a Sepa MG-17 membrane allowed a 87% retention of Gd 3+ and a 5% retention of La 3+ . The same nano-filtration-complexation system was experimented with an equimolar aqueous solution of Gd 3+ , Pr 3+ and La 3+ . Other experiments in the field of actinides(III)/lanthanides(III) separation were also performed. (authors)

Anomalous microstructural changes in III-nitrides under ion bombardment

International Nuclear Information System (INIS)

Kucheyev, S.O.; Williams, J.S.; Jagadish, C.

2002-01-01

Full text: Group-III nitrides (GaN, AlGaN, and InGaN) are currently a 'hot topic' in the physics and material research community due to very important technological applications of these materials in (opto)electronics. In the fabrication of III-nitride-based devices, ion bombardment represents a very attractive processing tool. However, ion-beam-produced lattice disorder and its undesirable consequences limit technological applications of ion implantation. Hence, studies of ion-beam-damage processes in Ill-nitrides are not only physically interesting but also technologically important. In this study, wurtzite GaN, AlGaN, and InGaN films exposed to ion bombardment under a wide range of irradiation conditions are studied by a combination of transmission electron microscopy (TEM), environmental scanning electron microscopy (ESEM), energy dispersive x-ray spectrometry (EDS), atomic force microscopy (AFM), cathodoluminescence (CL), and Rutherford backscattering/channeling (RBS/C) spectrometry. Results show that, unlike the situation for mature semiconductors such as Si and GaAs, Ill-nitrides exhibit a range of intriguing behavior involving extreme microstructural changes under ion bombardment. In this presentation, the following aspects are discussed: (i) formation of lattice defects during ion bombardment, (ii) ion-beam-induced phase transformations, (iii) ion-beam-produced stoichiometric imbalance and associated material decomposition, and (iv) an application of charging phenomena during ESEM imaging for studies of electrical isolation in GaN by MeV light ion irradiation. Emphasis is given to the (powerful) application of electron microscopy techniques for the understanding of physical processes occurring in Ill-nitrides under ion bombardment. Copyright (2002) Australian Society for Electron Microscopy Inc

Few atom chemistry of the trans actinide element rutherfordium (Rf)

International Nuclear Information System (INIS)

Nagame, Y.

2002-01-01

Studies of chemical properties of the trans actinide elements - starting with element 104 (Rf) - offer the unique opportunity to obtain information about trends in the Periodic Table at the limits of nuclear stability and to assess the magnitude of the influence of relativistic effects on chemical properties. To explore experimentally the influence of relativistic effects of electron shell structure, we study the chemical properties of the trans actinide elements. So far, we have developed some experimental apparatuses for the study of chemical properties of the trans actinide elements: a beam-line safety system for the usage of the gas-jet coupled radioactive 248 Cm target chamber for the production of trans actinides, a rotating wheel catcher apparatus for the measurement of α particles and spontaneous fission decay of trans actinides and an automated rapid chemical separation apparatus based on high performance liquid chromatography. The trans actinide nuclide, the element 104, 261 Rf (t 1/2 = 78 s) has been successfully produced via the reactions of 248 Cm( 18 O,5n) at the JAERI (Japan Atomic Energy Research Institute) tandem accelerator. The evaluated production cross section was about 10 nb, indicating that the production rate was approximately 2 atoms per min. Because of the short half-life and the low production rate of Rf, each atom produced decays before a new atom is synthesized. It means that any chemistry to be performed must be done on an 'atom-at-a-time' basis. Therefore rapid, very efficient and selective chemical procedures are indispensable to isolate the desired trans actinide 261 Rf. To perform fast and repetitive ion-exchange separation of Rf, we have developed the apparatus AIDA (Automated Ion exchange separation system coupled with the Detection apparatus for Alpha spectroscopy). Recently, ion-exchange behavior of Rf in acidic solutions has been studied with AIDA, and the results indicate that anion-exchange behavior of Rf is quite similar

Partnew - New solvent extraction processes for minor actinides - final report; Partnew - Nouveaux procedes d'extraction par solvant pour les actinides mineurs - rapport final

Energy Technology Data Exchange (ETDEWEB)

Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

2004-07-01

The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

Coprecipitation of aluminium with hydroxides of tetra-, penta- and hexavalent actinides

International Nuclear Information System (INIS)

Yusov, A.B.; Budantseva, N.A.; Anan'ev, A.V.; Fedoseev, A.M.

2000-01-01

By the methods of IR spectroscopy and powder x-ray diffractometry precipitates formed in alkaline medium by actinide (4, 5, 6) in the presence of aluminium are studied. It is shown that in studied conditions formation of actinide aluminates not occurs. In the same time in the process of precipitation interaction of aluminium hydroxocomplexes with U(6) and Th(4) ions probably takes place. Hypothesis is expressed that possibility of aluminium hydroxocomplexes interaction with actinides in different oxidation state is depended on peculiarities of hydrolytic behaviour of the lasts [ru

Separation and preconcentration of actinides from acidic media by extraction chromatography

International Nuclear Information System (INIS)

Horwitz, E. Philip; Chiarizia, Renato; Dietz, Mark L.; Diamond, Herbert; Nelson, Donald M.

1993-01-01

A systematic examination of the effect of nitric and hydrochloric acid concentrations and of macro levels of selected elements on the sorption of actinide ions by a novel extraction chromatographic resin comprised of a solution of octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide in tri-n-butyl phosphate supported on an inert polymeric substrate is described. Actinide sorption is demonstrated to be most efficient at high (>1 M) nitric acid concentrations, although tetra- and hexavalent actinides are strongly retained even from dilute (e.g., 0.05 M) nitric acid solutions. Macro concentrations of several common anions (e.g., PO 4 3- and SO 4 2- ) or complexing agents (e.g., oxalic acid) are shown not to adversely affect the sorption of trivalent actinides, while reducing the sorption of tetravalents. Such effects, together with oxidation state adjustments, are shown to provide a basis for the sequential elution of individual actinides and for actinide isolation from environmental and biological matrices

Organometallic neptunium(III) complexes

Science.gov (United States)

Dutkiewicz, Michał S.; Farnaby, Joy H.; Apostolidis, Christos; Colineau, Eric; Walter, Olaf; Magnani, Nicola; Gardiner, Michael G.; Love, Jason B.; Kaltsoyannis, Nikolas; Caciuffo, Roberto; Arnold, Polly L.

2016-08-01

Studies of transuranic organometallic complexes provide a particularly valuable insight into covalent contributions to the metal-ligand bonding, in which the subtle differences between the transuranium actinide ions and their lighter lanthanide counterparts are of fundamental importance for the effective remediation of nuclear waste. Unlike the organometallic chemistry of uranium, which has focused strongly on UIII and has seen some spectacular advances, that of the transuranics is significantly technically more challenging and has remained dormant. In the case of neptunium, it is limited mainly to NpIV. Here we report the synthesis of three new NpIII organometallic compounds and the characterization of their molecular and electronic structures. These studies suggest that NpIII complexes could act as single-molecule magnets, and that the lower oxidation state of NpII is chemically accessible. In comparison with lanthanide analogues, significant d- and f-electron contributions to key NpIII orbitals are observed, which shows that fundamental neptunium organometallic chemistry can provide new insights into the behaviour of f-elements.

Partnew - New solvent extraction processes for minor actinides - final report

International Nuclear Information System (INIS)

Madic, C.; Testard, F.; Hudson, M.J.; Liljenzin, J.O.; Christiansen, B.; Ferrando, M.; Facchini, A.; Geist, A.; Modolo, G.; Gonzalez-Espartero, A.; Mendoza, J. de

2004-01-01

The objectives of the European project PARTNEW were to define solvent extraction processes for the partitioning of the minor actinides, Am and Cm, from the aqueous high active raffinate or high active concentrate issuing the reprocessing of nuclear spent fuels by the PUREX process. Eleven laboratories participated to the research: 1/ CEA-DEN (Marcoule), 2/ CEA-DSM (Saclay), 3/ UREAD (U.K.), 4/ CTU (Sweden), 5/ ITU (Germany), 6/ ENEA (Italy), 7/ PoliMi (Italy), 8/ FZK-INE (Germany), 9/ FZJ-ISR (Germany), 10/ CIEMAT (Spain) and 11/ UAM (Spain). The research was organised into eight work packages (WP): Basic and applied DIAMEX studies, using diamide extractants for the co-extraction of actinides(III) (An(III)) and lanthanides(III) (Ln(III)) nitrates (WP1 and WP2), Basic and applied SANEX studies based on the use of polydentate N-ligands for the An(III)/Ln(III) separation (WP3 and WP4), Basic and applied SANEX studies based on the use of synergistic mixtures made of bis-(chloro-phenyl)-di-thio-phosphinic acid + neutral O-bearing ligand, (WP5 and WP6), Basic SANEX studies for the An(III)/Ln(III) separation, based on the use of new S-bearing ligands, Basic and applied studies for the Am(III)/Cm(III) separation. The work done in the fundamental and applied domains was very fruitful. Several processes have been successfully tested with genuine high active raffinates and concentrate. (authors)

Actinides and environmental interfaces: striving for molecular-level understanding

International Nuclear Information System (INIS)

Heino Nitsche

2005-01-01

Actinides can undergo a variety of complex chemical reactions in the environment. In addition to the formation of solid precipitates, colloids and dissolved solution species common to aqueous systems, actinide ions can interact with the surrounding geo and biomedia to change oxidation states or sorb on surfaces and colloids. The rate of migration is determined by aqueous solubility, and interactions with solid surfaces such as minerals, soils, natural organic matter, and soil microorganisms Sorption of aqueous actinide species on biological and geological matrices can be quantitatively described by a surface complexation or site-binding model. The disadvantage of this model is the difficulty in the experimental determination of the model parameters and surface reaction constants. Usually, a set of surface reactions and species are proposed based on knowledge of the solution speciation of the solute, and the reaction constants are usually derived by fitting computer-calculated absorption curves to experimental data. Because this process typically involves a large number of potentially adjustable parameters, it is likely to lead to non-unique parameter fitting and does not always result in a consistent set of parameters for the same systems. A fundamental molecular-level understanding of sorption processes of actinides on environmental surfaces is required to better understand and predict their transport behavior in nature. Several different surface spectroscopic techniques have been applied to the characterization of the adsorbed species and surface reactions and a direct determination of the sorbed species and surface reactions has become possible. The non-linear optical techniques of second harmonic and sum frequency generation (SHG and SFG) are ideally suited to study surfaces and interfaces of mineral oxides, biosurfactants and biopolymers, organic adlayers adsorbed on solid/mineral surfaces and soil organic matter, including humic and fulvic acids. Resonant

Evaluation of a polymer inclusion membrane containing a C-pivot tripodal diglycolamide for Am(III) extraction

International Nuclear Information System (INIS)

Mahanty, B.N.; Das, D.K.; Afzal, Md; Raut, D.R.; Mohapatra, P.K.; Behere, P.G.; Verboom, W.

2014-01-01

The instability of supported liquid membrane (SLM), being used for laboratory scale metal ion separation, can be avoided using Polymer inclusion membranes (PIM). We have been carrying out studies on diglycolamide based extractants including a C-pivot tripodal diglycolamide (T-DGA) for actinide ion separation from acidic feed solution. It was thought of interest to study the properties of T-DGA based PIM containing cellulose triacetate (CTA) as polymer and 2-nitrophenyl octyl ether (NPOE) as the plasticizer for Am(III) uptake and transport

Sorption of Cr(III) ion from aqueous solution by two kinds of modified diatomite.

Science.gov (United States)

Li, Er; Zeng, Xiangying

2012-01-01

Raw diatomite modified by microemulsion (DMM) and manganese oxide (MnD) were used for the removal of Cr(III) ions from aqueous solution. The characteristics and performance of these two types of modified diatomite on Cr(III) ion adsorption were compared. The results indicate that the Cr(III) ion adsorption capacities of diatomite were considerably improved after modifications by manganese oxide (MnO) and microemulsion. The surface area of MnD was increased because of the formation of MnO on the diatomite surface, and that of DMM was promoted owing to the existence of the hydrolyzed aromatic acid. Because of the stronger surface ionized function, the adsorption performance of Cr(III) ions in DMM was better than that in MnD. Within the experimental range of pH (i.e. 2.2-6.3), the Cr(III) ion removal of DMM (35-70%) was higher than that of MnD (33-59%) owing to the different electrostatic forces between the Cr(III) ion and the surface of the modified diatomite. The Cr(III) ion removal in MnD and DMM was improved with the increase of synthetic solution concentration in volumes from 0 to 2,500 mL.

Rare earths and actinides

International Nuclear Information System (INIS)

Coqblin, B.

1982-01-01

This paper reviews the different properties of rare-earths and actinides, either as pure metals or as in alloys or compounds. Three different cases are considered: (i) First, in the case of 'normal' rare-earths which are characterized by a valence of 3, we discuss essentially the magnetic ordering, the coexistence between superconductivity and magnetism and the properties of amorphous rare-earth systems. (ii) Second, in the case of 'anomalous' rare-earths, we distinguish between either 'intermediate-valence' systems or 'Kondo' systems. Special emphasis is given to the problems of the 'Kondo lattice' (for compounds such as CeAl 2 ,CeAl 3 or CeB 6 ) or the 'Anderson lattice' (for compounds such as TmSe). The problem of neutron diffraction in these systems is also discussed. (iii) Third, in the case of actinides, we can separate between the d-f hybridized and almost magnetic metals at the beginning of the series and the rare-earth like the metals after americium. (orig.)

Extraction of trivalent actinides and lanthanides from nitric acid solutions by ion flotation

International Nuclear Information System (INIS)

Mezhov, E.H.; Samatov, A.V.; Troyanovskiy, L.V.

1992-01-01

To determine whether the deep extraction of trivalent actinides from liquid active waste is feasible, the authors made a detailed investigation into the ion flotation of europium (as a simulator of americium) and americium from nitric acid solutions by using as an SAS precipitant either lauril phosphoric acid (LPA) to reprocess 0.1-0.7 M HNO 3 or diphosphine dioxides (PO) for 1-5 M HNO 3 . In all instances the extent of metal removal increases with floto-reagent expenditure. When the floto-reagent excess required for full precipitation is reached, the extraction of the metals under study is high, viz., 97-98% from 0.1 M HNO 3 with LPA and ∼75% from 3-3.5 M HNO 3 with PO per one flotation operation

Stability constants of the fluoride complexes of actinides in aqueous solution and their correlation with fundamental properties

International Nuclear Information System (INIS)

Chaudhuri, N.K.; Sawant, R.M.

1997-09-01

Stability constants of the fluoride complexes of the actinides in different oxidation states measured by potentiometric method using fluoride ion selective electrode have been presented. Procedure and precautions required to overcome certain difficulties particular to actinide ions have been discussed. Literature data from various sources have been compiled. In order to have a reasonable comparison the stability constant (β 1 ) values obtained in diverse ionic strength media are converted to thermodynamic stability constant, β 1 0 , using Davies equation (a modification of Debye-Huckel equation). A correlation of the β 1 0 values with the fundamental properties of the actinide ions using various models available in the literature has been attempted. A semiempirical relation recently developed by Brown, Sylva and Ellis (BSE equation) appears to be most suitable. Using the values of ionic radii and best available values of the stability constants of a large number of metal ions from recent compilations a comparative study of the various models or relations available in the literature has been tried. For metal ions in general, the best correlation is obtained with the BSE equation. In an attempt to accommodate the unusual trend in the stability constants of the tetravalent actinides a modification in a parameter of the BSE equation has been proposed. Good agreement between the theoretically calculated and experimentally determined values for actinides in different oxidation states is then obtained in most of the cases. (author)

Kinetic Study on the Sorption of Te (IV), Ce (III) and Eu (III) on some Inorganic Ion Exchangers

International Nuclear Information System (INIS)

El-Sweify, F.H.; Shehata, M.K.K.; El-Shazly, E.A.A.

2008-01-01

The sorption behaviour of Te (IV), Ce (III) and Eu (III) on zirconium phosphate (Zr P) and ceric tungstate under various conditions was studied. Some factors affecting the sorption kinetics of the aforementioned metal ions on both ion exchangers were investigated. These factors were: hydrogen ion concentration in the absence of complexing agents, contact time, particle size of the two mentioned ion exchangers, metal in concentration and temperature. Radioactive isotopes were used for tracing the corresponding elements. Some physical parameters related to the sorption process were calculated from the obtained data

Applications of inorganic ion exchangers; I-sorption and fixation of some radionuclides in synthetic iron (III)titanate ion exchanger

International Nuclear Information System (INIS)

Abou-Mesalam, M.M.; El-Naggar, I.M.

2002-01-01

Iron(III) titanate as inorganic ion exchange material has been synthesized by addition of ferric nitrate solution to titanium tetrachloride (dissolved in 4M HCI) with molar ratio equal to unity. The data obtained proposed that the chemical formula of iron(III) titanate may written either as Fe 1 .3 (TiO). 2h 2 O or Fe(TiO 4 ) 0 .76.1.5H 2 O. The surface area values of unloaded and loaded iron(III) titanate with Cs + , Co 2 + and Eu 3 + ions were measured using BET-technique. The selectiy sequence for sorption of Cs + , Co 2 + and Fu 3 + ions on iron (III) titanate was found to be; Co 2 + > Eu 3 + > Cs + . The leach rate values of Cs + , Co 2 + and Fu 3 + ions from iron (II) titanate heated to 1000 degree C different leachants were determined and shows lower values compared to those obtained from unheated iron (III) titanate (dried at 50 degree C) which elucidate the suitability of iron (III) titanate in fixation of Cs + , Co 2 + and Eu 3 + ions by thermal treatment up to1000 degree.

Diglycolamide based dendrimers for sequestration of trivalent actinides: solvent extraction and liquid membrane studies

International Nuclear Information System (INIS)

Ansari, S.A.; Mohapatra, P.K.; Leoncini, A.; Verboom, W.

2017-01-01

Three diglycolamide-functionalized (poly(propylene imine)) diaminobutane dendrimers, viz. zero generation (L_I), first generation (L_I_I), and second generation (L_I_I_I), were synthesized and evaluated for their extraction ability towards trivalent actinides. The distribution ratio (D) of Am"3"+ with 1.0 mmol/L ligand at 3 M HNO_3 followed the order: 0.1 (L_I) < 42 (L_I_I) < 110 (L_I_I_I). The D values of Am(_I_I_I) at lower acidity (0.01 M HNO_3) were significantly low, giving good stripping option with the dilute acid solution. Extraction of other metal ions from 3 M HNO_3 indicated good selectivity of Am(III) over U(VI), Sr(II) and Cs(I). Supported liquid membrane (SLM) studies were explored for the transport of Am(III) from acidic feed solution, where ligand inventory is extremely low. (author)

Organophosphorus reagents in actinide separations: Unique tools for production, cleanup and disposal

International Nuclear Information System (INIS)

Nash, K. L.

2000-01-01

Interactions of actinide ions with phosphate and organophosphorus reagents have figured prominently in nuclear science and technology, particularly in the hydrometallurgical processing of irradiated nuclear fuel. Actinide interactions with phosphorus-containing species impact all aspects from the stability of naturally occurring actinides in phosphate mineral phases through the application of the bismuth phosphate and PUREX processes for large-scale production of transuranic elements to the development of analytical separation and environment restoration processes based on new organophosphorus reagents. In this report, an overview of the unique role of organophosphorus compounds in actinide production, disposal, and environment restoration is presented. The broad utility of these reagents and their unique chemical properties is emphasized

The complex formation of selected actinides (U, Np, Cm) with microbial ligands

International Nuclear Information System (INIS)

Glorius, Maja

2009-01-01

One of the urgent tasks in the field of nuclear technology is the final storage of radioactive substances. As a part of the safety requirements the protection of humans and the environment from the danger of radioactive substances in case of the release from the final storage is essential. For performing long-term safety calculations the detailed understanding of the physico-chemical effects and influences which cause the mobilisation and transport of actinides are necessary. The presented work was a discrete part of a project, which was focused on the clarification of the influence of microorganisms on the migration of actinides in case of the release of actinides from a final storage. The influence of microbial produced substances on the mobilisation of selected actinides was studied thereby. The microbial produced substances studied in this project were synthesized by bacteria from the Pseudomonas genus under special conditions. Fluorescent Pseudomonads secrete bacterial pyoverdin-type siderophores with a high potential to complex and transport metals, especially iron(III). The aim of the project was to determine how and under which conditions the bioligands are able to complex also radioactive substances and therefore to transport them. For this work the alpha-emitting actinides uranium, curium and neptunium were chosen because their long-life cycle and their radiotoxicity are a matter of particular interest. This work dealed with the interaction of the actinides U(VI), Np(V) and Cm(III) with model ligands simulating the functionality of the pyoverdins. So, such bioligands can essentially influence the behaviour of actinides in the environment. The results of this work contribute to a better understanding and assessment of the influence of the microbial ligands to the mobilisation and migration of the radionuclides. The outcomes could be used to quantify the actinide-mobilising effect of the bioligands, which are released, for example, in the vicinity of a

Process of converting actinide ions present in the solid residues of a sulphating process for radioactive solid waste containing actinides into a useful state

International Nuclear Information System (INIS)

Wieczorek, H.; Oser, B.

1985-01-01

Stages of the process: a) The residue is dissolved in water or 1 to 2 mole nitric acid, where the greater part is dissolved. b) The solution formed is separated from the insoluble part of the residue and is heated to a temperature below its boiling point. c) The hot solution has an aquaeous barium nitrate solution added to it with a quantity which slightly exceeds that required for the stochiometric complete precipitation of the sulphate ions. The solution is kept at the selected temperature for a period of 0.5 to 2 hours. d) After subsequent cooling to room temperature, the precipitated barium sulphate is separated and e) the actinide-nitrate solution is fed into an extractive reprocessing process. (orig./PW) [de

A time-resolved laser fluorescence spectroscopy (TRLFS) study of the interaction of trivalent actinides (curium(III)) with calcite

International Nuclear Information System (INIS)

Stumpf, Th.; Fanghaenel, Th.

2002-01-01

Cm(III) interaction with calcite was investigated in the trace concentration range. Two different Cm(III)/calcite sorption species were found. The first Cm(III) sorption species consists of a curium ion that is bonded onto the calcite surface. The second Cm(III) sorption species has lost its complete hydration sphere and is incorporated into the calcite bulk structure /1/. (orig.)

Electronic structure of free and doped actinides: N and Z dependences of energy levels and electronic structure parameters

International Nuclear Information System (INIS)

Kulagin, N.

2005-01-01

Theoretical study of electronic structure of antinide ions and its dependence on N and Z are presented in this paper. The main 5f N and excited 5f N n'l' N' configurations of actinides have been studied using Hartree-Fock-Pauli approximation. Results of calculations of radial integrals and the energy of X-ray lines for all 5f ions with electronic state AC +1 -AC +4 show approximate dependence on N and Z. A square of N and cubic of Z are ewalized for the primary electronic parameters of the actinides. Theoretical values of radial integrals for free actinides and for ions in a cluster AC +n :[L] k are compared, too

A systematic study of actinide production from the interactions of heavy ions with sup 248 Cm

Energy Technology Data Exchange (ETDEWEB)

Leyba, J.D.

1990-09-07

Production cross sections for heavy actinides produced from the interactions of {sup 12}C, {sup 31}P, {sup 40}Ar, and {sup 44}Ca ions with {sup 248}Cm were measured at energies ranging from 0.98 to 1.35 X Coulomb barrier. The recoiling reaction products were collected in copper or gold catcher foils located near the {sup 248}Cm target. Separate fractions of Bk, Cf, Es, Fm, and Md were obtained from a radiochemical separation procedure. For the {sup 12}C system, a He/KCl jet was used to transport the recoiling No activities of interest to a rotating wheel system. The isotopic distributions of the actinide products were found to be essentially symmetric about the maximum with full-widths-at-half-maximum of approximately 2.5 mass units. Isotopic distributions of the {sup 12}C, {sup 31}P, {sup 40}Ar, and {sup 44}Ca systems were found to be very similar to the {sup 40,48}Ca systems studied previously. The maxima of the isotopic distributions generally occurred for those reaction channels which involved the exchange of the fewest number of nucleons between the target and projectile for which the calculated excitation energy was a positive quantity. Additionally, the maxima of the excitation functions occurred at those projectile energies which were consistent with the calculated reaction barriers based upon a binary reaction mechanism. The experimental data from the four systems investigated were compared to several models of heavy ion interactions including a damped reaction mechanism, compound nucleus formation and subsequent particle evaporation, and classical partial wave calculations for binary systems.

Sorption Speciation of Lanthanides/Actinides on Minerals by TRLFS, EXAFS and DFT Studies: A Review

Directory of Open Access Journals (Sweden)

Xiaoli Tan

2010-11-01

Full Text Available Lanthanides/actinides sorption speciation on minerals and oxides by means of time resolved laser fluorescence spectroscopy (TRLFS, extended X-ray absorption fine structure spectroscopy (EXAFS and density functional theory (DFT is reviewed in the field of nuclear disposal safety research. The theoretical aspects of the methods are concisely presented. Examples of recent research results of lanthanide/actinide speciation and local atomic structures using TRLFS, EXAFS and DFT are discussed. The interaction of lanthanides/actinides with oxides and minerals as well as their uptake are also of common interest in radionuclide chemistry. Especially the sorption and inclusion of radionuclides into several minerals lead to an improvement in knowledge of minor components in solids. In the solid-liquid interface, the speciation and local atomic structures of Eu(III, Cm(III, U(VI, and Np(IV/VI in several natural and synthetic minerals and oxides are also reviewed and discussed. The review is important to understand the physicochemical behavior of lanthanides/actinides at a molecular level in the natural environment.

Actinide metal processing

International Nuclear Information System (INIS)

Sauer, N.N.; Watkin, J.G.

1992-01-01

A process for converting an actinide metal such as thorium, uranium, or plutonium to an actinide oxide material by admixing the actinide metal in an aqueous medium with a hypochlorite as an oxidizing agent for sufficient time to form the actinide oxide material and recovering the actinide oxide material is described together with a low temperature process for preparing an actinide oxide nitrate such as uranyl nitrate. Additionally, a composition of matter comprising the reaction product of uranium metal and sodium hypochlorite is provided, the reaction product being an essentially insoluble uranium oxide material suitable for disposal or long term storage

Multiscale structural characterizations of mixed U(iv)-An(iii) oxalates (An(iii) = Pu or Am) combining XAS and XRD measurements.

Science.gov (United States)

Arab-Chapelet, B; Martin, P M; Costenoble, S; Delahaye, T; Scheinost, A C; Grandjean, S; Abraham, F

2016-04-28

Mixed actinide(III,IV) oxalates of the general formula M2.2UAn(C2O4)5·nH2O (An = Pu or Am and M = H3O(+) and N2H5(+)) have been quantitatively precipitated by oxalic precipitation in nitric acid medium (yield >99%). Thorough multiscale structural characterization using XRD and XAS measurements confirmed the existence of mixed actinide oxalate solid solutions. The XANES analysis confirmed that the oxidation states of the metallic cations, tetravalent for uranium and trivalent for plutonium and americium, are maintained during the precipitation step. EXAFS measurements show that the local environments around U(+IV), Pu(+III) and Am(+III) are comparable, and the actinides are surrounded by ten oxygen atoms from five bidentate oxalate anions. The mean metal-oxygen distances obtained by XAS measurements are in agreement with those calculated from XRD lattice parameters.

Synthesis of tetravalent actinide chlorides. Versatile compounds for actinide chemistry

Energy Technology Data Exchange (ETDEWEB)

Maerz, Juliane [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements

2016-07-01

Anhydrous actinide tetrachlorides (AnCl{sub 4}) were synthesized under mild conditions to provide versatile compounds for actinide chemistry. They enable a direct access to actinide complexes with organic and inorganic ligands.

Synergistic extraction of Eu(III) with N-phosphorylated bis-ureas and chlorinated cobalt bis(dicarbollide) ion

Czech Academy of Sciences Publication Activity Database

Selucký, P.; Bubeníková, M.; Rais, J.; Grüner, Bohumír; Brusko, V.V.

2013-01-01

Roč. 101, č. 1 (2013), s. 27-31 ISSN 0033-8230 R&D Projects: GA ČR GA104/09/0668 Institutional support: RVO:61388980 Keywords : liquid-liquid extraction * lanthanides * actinides * N-phosphorylated bis-ureas * chlorinated cobalt bis(dicarbollide) ion * high level liquid waste Subject RIV: CA - Inorganic Chemistry Impact factor: 1.411, year: 2013

Polymer Inclusion Membrane Containing a Tripodal Diglycolamide Ligand: Actinide Ion Uptake and Transport Studies

NARCIS (Netherlands)

Mahanty, B.; Mohapatra, P.K.; Raut, D.R.; Das, D.K.; Behere, P.G.; Afzal, M.; Verboom, Willem

2016-01-01

A cellulose triacetate (CTA)-based polymer inclusion membrane (PIM) containing a C-pivot tripodal diglycolamide (T-DGA) as the carrier extractant and 2-nitrophenyl octyl ether (NPOE) as the plasticizer shows potential for the uptake of actinides from acidic feed solutions. The uptake of actinides

TAILORING INORGANIC SORBENTS FOR SRS STRONTIUM AND ACTINIDE SEPARATIONS: MODIFIED MONOSODIUM TITANATE PHASE III FINAL REPORT

Energy Technology Data Exchange (ETDEWEB)

Taylor-Pashow, K.; Hobbs, D.

2010-09-01

This document provides a final report of Phase III testing activities for the development of modified monosodium titanate (mMST), which exhibits improved strontium and actinide removal characteristics compared to the baseline MST material. The activities included characterization of the crystalline phases present at varying temperatures, solids settling characteristics, quantification of the peroxide content; evaluation of the post-synthesis gas release under different conditions; the extent of desorption of {sup 85}Sr, Np, and Pu under washing conditions; and the effects of age and radiation on the performance of the mMST. Key findings and conclusions include the following. The peroxide content of several mMST samples was determined using iodometric titration. The peroxide content was found to decrease with age or upon extended exposure to elevated temperature. A loss of peroxide was also measured after exposure of the material to an alkaline salt solution similar in composition to the simulated waste solution. To determine if the loss of peroxide with age affects the performance of the material, Sr and actinide removal tests were conducted with samples of varying age. The oldest sample (4 years and 8 months) did show lower Sr and Pu removal performance. When compared to the youngest sample tested (1 month), the oldest sample retained only 15% of the DF for Pu. Previous testing with this sample indicated no decrease in Pu removal performance up to an age of 30 months. No loss in Np removal performance was observed for any of the aged samples, and no uptake of uranium occurred at the typical sorbent loading of 0.2 g/L. Additional testing with a uranium only simulant and higher mMST loading (3.0 g/L) indicated a 10% increase of uranium uptake for a sample aged 3 years and 8 months when compared to the results of the same sample measured at an age of 1 year and 5 months. Performance testing with both baseline-MST and mMST that had been irradiated in a gamma source to

Study on the leaching behavior of actinides from nuclear fuel debris

Science.gov (United States)

Kirishima, Akira; Hirano, Masahiko; Akiyama, Daisuke; Sasaki, Takayuki; Sato, Nobuaki

2018-04-01

For the prediction of the leaching behavior of actinides contained in the nuclear fuel debris generated by the Fukushima Daiichi nuclear power plant accident in Japan, simulated fuel debris consisting of a UO2-ZrO2 solid solution doped with 137Cs, 237Np, 236Pu, and 241Am tracers was synthesized and investigated. The synthesis of the debris was carried out by heat treatment at 1200 °C at different oxygen partial pressures, and the samples were subsequently used for leaching tests with Milli-Q water and seawater. The results of the leaching tests indicate that the leaching of actinides depends on the redox conditions under which the debris was generated; for example, debris generated under oxidative conditions releases more actinide nuclides to water than that generated under reductive conditions. Furthermore, we found that, as Zr(IV) increasingly substituted U(IV) in the fluorite crystal structure of the debris, the actinide leaching from the debris decreased. In addition, we found that seawater leached more actinides from the debris than pure water, which seems to be caused by the complexation of actinides by carbonate ions in seawater.

Elaboration of extracting, incinerable and/or conducting resins, for the grouped conversion of actinides; Conception de resines extractantes, incinerables et/ou conductrices, pour la conversion groupee d'actinides

Energy Technology Data Exchange (ETDEWEB)

Mokhtari, H. [Paris-11 Univ., 91 - Orsay (France)]|[CEA Valrho, Lab. de Chimie des Actinides (LCA), 30 - Marcoule (France)

2006-07-01

The first results obtained in the framework of the study called PEACE (Process for the Elaboration of Actinide Carbide from ion Exchange resin) concern the fixation of neodymium(III) (simulating trivalent actinides) on two carboxylic resins: the first one is of gel type and the second one of macroporous type. A kinetic study of the exchange NH{sub 4}{sup +}/Nd{sup 3+} has shown that: 1)neodymium is fixed under the form of a complexed or hydrolyzed specie of neodymium of charge 2+ 2)a high charge rate is reached (40% in mass for the dried resin which corresponds to an exchange capacity of 11 meq/g dry of introduced resin) 3)the exchange kinetics is better for the macroporous resin than for the gel resin. A heat treatment of the macroporous resin charged in neodymium has been carried out until the carbonization by the mean of thermal gravimetric analyses carried out under air and argon. A carbon/neodymium ratio of about 5 is obtained after carbonization under argon. Scanning electron microscopy analyses carried out on the macroporous resin charged in neodymium have revealed a conservation of the sphericity and a consequent reduction of the resin balls diameter after heat treatment and an homogeneous distribution of neodymium inside the sphere. (O.M.)

U(VI) and Eu(III) ion sorption in the interface solution-phosphate solids: Structural study and mechanisms

International Nuclear Information System (INIS)

Drot, Romuald

1998-01-01

As part of the storage of nuclear wastes in a deep underground disposal, radionuclides sorption on geological or engineered barriers is one of the most important factor which could enhance retardation. Thus, the knowledge of such mechanisms is needed. For this purpose, we chose to experimentally define sorption equilibria before performing simulation of retention data. Several phosphate compounds are potential candidates as engineered barrier additives. We considered Th 4 (PO 4 ) 4 P 2 O 7 , Zr 2 O(PO 4 ) 2 which allow to study the effect of PO 4 and P 2 O 7 groups separately. Eu(III) and U(IV) ions were used as structural probes in order to simulate actinides (III) and (VI) behavior. X-ray powder diffraction, IR spectroscopy and electron probe microanalysis were used to characterized the synthesized solids. Electrophoretic measurements showed an amphoteric behavior of surface sites. Moreover, laser spectro-fluorimetry experiments indicated that no diffusion phenomena of the sorbed ion inside the solid occurs. Thus, we considered that a surface complexation model should be applied. Laser spectro-fluorimetry and XPS allowed to determine the nature of surface sites. ZrP 2 O 7 presents only one single site (P 2 O 7 groups) whereas Th 4 (PO 4 ) 4 P 2 O 7 and Zr 2 O(PO 4 ) 2 admit two types of sites (PO 4 /P 2 O 7 and PO 4 /oxo groups, respectively). Sorbed species were identified using laser spectro-fluorimetry which indicate that, in KNO 3 0.5 M medium and for a known surface site, there are two surface complexes for U(VI) (sorption of UO 2+ 2 et de UO 2 NO + 3 species) and only one for Eu(III) (sorption of EuNO 2+ 3 ). They are linked to the substrate as bidentate inner sphere complexes (EXAFS study). Surface acidity constants were determined by simulation of potentiometric titration curves obtained for each solid suspension using FITEQL code (CCM). As sorption equilibria were defined, experimental retention data simulation was performed with respect to structural

Structure and luminescent property of complexes of aryl carboxylic acid-functionalized polystyrene with Eu(III) and Tb(III) ions.

Science.gov (United States)

Gao, Baojiao; Shi, Nan; Qiao, Zongwen

2015-11-05

Via polymer reactions, naphthoic acid (NA) and benzoic acid (BA) were bonded onto the side chains of polystyrene (PS), respectively, and two aryl carboxylic acid-functionalized polystyrenes, PSNA and PSBA, were obtained. Using PSNA and PSBA as macromolecule ligands and Eu(3+) and Tb(3+) ions as central ions, various luminescent binary polymer-rare earth complexes were prepared. At the same time, with 1,10-phenanthroline (Phen) and 4,4'-bipyridine (Bipy) as small-molecule co-ligands, various ternary polymer-rare earth complexes were also prepared. On the basis of characterizing PSNA, PSBA and complexes, the relationship between structure and luminescent property for these prepared complexes were mainly investigated. The study results show that the macromolecule ligands PSNA and PSBA, or the bonded NA and BA ligands, can strongly sensitize the fluorescence emissions of Eu(3+) ion or Tb(3+) ion, but the sensitization effect is strongly dependent on the structure of the ligands and the property of the central ions, namely it is strongly dependent on the matching degree of energy levels. The fluorescence emission of the binary complex PS-(NA)3-Eu(III) is stronger than that PS-(BA)3-Eu(III), indicating ligand NA has stronger sensitization action for Eu(3+) ion than ligand BA; the binary complex PS-(BA)3-Tb(III) emit strong characteristic fluorescence of Tb(3+) ion, displaying that ligand BA can strongly sensitize Tb(3+) ion, whereas the binary complex PS-(NA)3-Tb(III) nearly does not emit the characteristic fluorescence of Tb(3+) ion, showing that ligand NA does not sensitize Tb(3+) ion. The fluorescence intensity of the ternary complexes is much stronger than that of the binary complexes in the same series. Copyright © 2015 Elsevier B.V. All rights reserved.

Aqueous complexes of lanthanides(III) and actinides(III) with the carbonate and sulphate ions. Thermodynamic study by time-resolved laser-induced fluorescence spectroscopy and electro-spray-ionisation mass spectrometry; Complexes aqueux de lanthanides (3) et actinides (3) avec les ions carbonate et sulfate. Etude thermodynamique par spectrofluorimetrie laser resolue en temps et spectrometrie de masse a ionisation electrospray

Energy Technology Data Exchange (ETDEWEB)

Vercouter, Th

2005-03-15

The prediction of the environmental impact of a possible geological disposal of radioactive wastes is supported by the thermodynamic modelling of the radionuclides behaviour in the groundwater. In this framework, the analogy between lanthanides and actinides(III) is confirmed by a critical analysis of the literature and the comparison with experimental results obtained here. The limiting complex, Eu(CO{sub 3}){sub 3}{sup 3-}, is identified by solubility measurements in Na{sub 2}CO{sub 3} solutions. Then the formation constants of the complexes Eu(CO{sub 3}){sub i}{sup 3-2i} (i=1-3) and Eu(SO{sub 4}){sub i}{sup 3-2i} (i=1-2) are measured by TRLFS. The formation of aqueous LaSO{sub 4}{sup +} is studied by ESI-MS and is in good agreement with the expected speciation. The enthalpy and entropy of the reaction Cm(CO{sub 3}){sub 2}{sup -} + CO{sub 3}{sup 2-} {r_reversible} Cm(CO{sub 3}){sub 3}{sup 3-} are deduced from TRLFS measurements of the equilibrium constant between 10 and 70 C. The ionic strength effect is calculated using the SIT formula. (author)

Development and demonstration of innovative partitioning processes (i-SANEX and 1-cycle SANEX) for actinide partitioning

International Nuclear Information System (INIS)

Wilden, Andreas; Modolo, Giuseppe; Geist, Andreas

2015-01-01

For the recovery of the trivalent actinides Am(III) and Cm(III) from PUREX raffinate, two innovative partitioning processes were developed within the European project ACSEPT. In the 'innovative-SANEX' concept, trivalent actinides (An(III)) and lanthanides (Ln(III)) are co-extracted by a TODGA-based solvent, which is then subjected to several stripping steps: selective stripping of An(III) with the hydrophilic ligand SO 3 -Ph-BTP, followed by subsequent stripping of Ln(III). A more challenging route studied also within our laboratories is the direct An(III) separation using a mixture of CyMe 4 BTBP and TODGA, the so-called '1-cycle SANEX' process. Both processes have been successfully demonstrated using spiked simulate solutions in laboratory-scale miniature annular centrifugal contactors using 32-stages flowsheets. The process development and results of the demonstration tests will be presented and discussed. Both processes showed a high recovery of An(III) with high fission-product decontamination factors. The safety of these processes is studied within the current European project SACSESS. (authors)

Complexes of actinides with naturally occuring organic substances - Literature survey

International Nuclear Information System (INIS)

Olofsson, U.; Allard, B.

1983-02-01

Properties of naturally occurring humic and fulvic acids and their formation of actinide complexes are reviewed. Actinides in all the oxdation states III, IV, V and VI would form complexes with many humic and fulvic acids, comparable in strength to the hydroxide and carbonate complexes. Preliminary experiments have shown, that the presence of predominantly humic acid complexes would significantly reduce the sorption of americium on geologic media. This does not, however, necessarily lead to a potentially enhanced mobility under environmental conditions, since humic and fulvic acids carrying trace metals also would be strongly bound to e.g. clayish material. (author)

Actinide separation by electrorefining

International Nuclear Information System (INIS)

Fusselman, S.P.; Gay, R.L.; Grantham, L.F.; Grimmett, D.L.; Roy, J.J.; Inoue, T.; Hijikata, T.; Krueger, C.L.; Storvick, T.S.; Takahashi, N.

1995-01-01

TRUMP-S is a pyrochemical process being developed for the recovery of actinides from PUREX wastes. This paper describes development of the electrochemical partitioning step for recovery of actinides in the TRUMP-S process. The objectives are to remove 99 % of each actinide from PUREX wastes, with a product that is > 90 % actinides. Laboratory tests indicate that > 99 % of actinides can be removed in the electrochemical partitioning step. A dynamic (not equilibrium) process model predicts that 90 wt % product actinide content can be achieved through 99 % actinide removal. Accuracy of model simulation results were confirmed in tests with rare earths. (authors)

Study of irradiation effects in perovskite: use of this matrix for actinides conditioning; Effets de l'irradiation dans une perovskite: utilisation de cette matrice pour un conditionnement des actinides

Energy Technology Data Exchange (ETDEWEB)

Sabathier, C

2003-07-01

The aim of this work is to study a specific conditioning matrix (ceramics) for actinides: the strontium titanate. At first, the choice of strontium titanate is discussed as well as its structure and its ability to incorporate actinides. The different studies carried out on the irradiation effects on the strontium titanate are reviewed. The main ion-matter interactions considered in the energy range used during our experiments are given. The different devices and techniques used with ion beams to carry out our experiments according to the type of sample: monocrystal or polycrystal are described. The experimental results on the behaviour of strontium titanate in terms of irradiation, temperature and ion flux used to damage the matrix are presented. The experimental results on the different steps of strontium titanate annealing are given as well as the identifying of the defects by different analyses techniques (Rutherford backscattering spectroscopy, transmission electron spectroscopy and x-rays spectroscopy). At last, a model of the behaviour of the strontium titanate in the case of an actinide conditioning is proposed and the evolving of the strontium titanate disorder during the storage is discussed. (O.M.)

Swedish-German actinide migration experiment at ÄSPÖ hard rock laboratory

Science.gov (United States)

Kienzler, B.; Vejmelka, P.; Römer, J.; Fanghänel, E.; Jansson, M.; Eriksen, T. E.; Wikberg, P.

2003-03-01

Within the scope of a bilateral cooperation between Svensk Kärnbränslehantering (SKB) and Forschungszentrum Karlsruhe, Institut für Nukleare Entsorgung (FZK-INE), an actinide migration experiment is currently being performed at the Äspö Hard Rock Laboratory (HRL) in Sweden. This paper covers laboratory and in situ investigations on actinide migration in single-fractured granite core samples. For the in situ experiment, the CHEMLAB 2 probe developed by SKB was used. The experimental setup as well as the breakthrough of inert tracers and of the actinides Am, Np and Pu are presented. The breakthrough curves of inert tracers were analyzed to determine hydraulic properties of the fractured samples. Postmortem analyses of the solid samples were performed to characterize the flow path and the sorbed actinides. After cutting the cores, the abraded material was analyzed with respect to sorbed actinides. The slices were scanned optically to visualize the flow path. Effective volumes and inner surface areas were measured. In the experiments, only breakthrough of Np(V) was observed. In each experiment, the recovery of Np(V) was ≤40%. Breakthrough of Am(III) and Pu(IV) as well as of Np(IV) was not observed.

Seventeen-coordinate actinide helium complexes

Energy Technology Data Exchange (ETDEWEB)

Kaltsoyannis, Nikolas [School of Chemistry, The University of Manchester (United Kingdom)

2017-06-12

The geometries and electronic structures of molecular ions featuring He atoms complexed to actinide cations are explored computationally using density functional and coupled cluster theories. A new record coordination number is established, as AcHe{sub 17}{sup 3+}, ThHe{sub 17}{sup 4+}, and PaHe{sub 17}{sup 4+} are all found to be true geometric minima, with the He atoms clearly located in the first shell around the actinide. Analysis of AcHe{sub n}{sup 3+} (n=1-17) using the quantum theory of atoms in molecules (QTAIM) confirms these systems as having closed shell, charge-induced dipole bonding. Excellent correlations (R{sup 2}>0.95) are found between QTAIM metrics (bond critical point electron densities and delocalization indices) and the average Ac-He distances, and also with the incremental He binding energies. (copyright 2017 Wiley-VCH Verlag GmbH and Co. KGaA, Weinheim)

Final Project Report for ER15351 ''A Study of New Actinide Zintl Ions Materials''

International Nuclear Information System (INIS)

Peter K. Dorhout

2007-01-01

The structural chemistry of actinide main-group metal materials provides the fundamental basis for the understanding of structural coordination chemistry and the formation of materials with desired or predicted structural features. The main-group metal building blocks, comprising sulfur-group, phosphorus-group, or silicon-group elements, have shown versatility in oxidation state, coordination, and bonding preferences. These building blocks have allowed us to elucidate a series of structures that are unique to the actinide elements, although we can find structural relationships to transition metal and 4f-element materials. In the past year, we investigated controlled metathesis and self-propagating reactions between actinide metal halides and alkali metal salts of main-group metal chalcogenides such as K-P-S salts. Ternary plutonium thiophosphates have resulted from these reactions at low temperature in sealed ampules. we have also focused efforts to examine reactions of Th, U, and Pu halide salts with other alkali metal salts such as Na-Ge-S and Na-Si-Se and copper chloride to identify if self-propagating reactions may be used as a viable reaction to prepare new actinide materials and we prepared a series of U and Th copper chalcogenide materials. Magnetic measurements continued to be a focus of actinide materials prepared in our laboratory. We also contributed to the XANES work at Los Alamos by preparing materials for study and for comparison with environmental samples

EUROPART: an European integrated project on actinide partitioning

International Nuclear Information System (INIS)

Madic, C.; Baron, P.; Hudson, M.J.

2006-01-01

Full text of publication follows: The EUROPART project is a scientific integrated project between 24 European partners, from 10 countries, mostly funded by the European Community within the FP6, together with CRIEPI from Japan and ANSTO from Australia. EUROPART aims at developing chemical partitioning processes for the so-called minor actinides (MA) contained in nuclear wastes, i.e. from Am to Cf. In the case of the treatment of dedicated spent fuels or targets, the actinides to be separated also include U, Pu and Np. The techniques considered for the separation of these radionuclides belong to the fields of hydrometallurgy and pyrometallurgy, as in the previous European FP5 programs named PARTNEW, CALIXPART and PYROREP, respectively. The two main axes of research within EUROPART are: 1/ the partitioning of MA (from Am to Cf) from wastes issuing from the reprocessing of high burn-up UOX fuels and multi-recycled MOX fuels, 2/ the partitioning of the whole actinide family of elements for recycling, as an option for advanced dedicated fuel cycles (this work will be connected to the studies to be performed within the EUROTRANS European integrated project). In hydrometallurgy, the research is organized in five Work Packages (WP). Four are dedicated to the study of partitioning methods mainly based on the use of solvent extraction methods and of solid extractants, one WP is dedicated to the development of actinide co-conversion methods for fuel or target preparations. The research in pyrometallurgy is organized into four WPs, listed hereafter: (i) study of the basic chemistry of transuranium elements and of some fission products in molten salts (chlorides, fluorides), (ii) development of actinide partitioning methods, (iii) study of the conditioning of the salt wastes, (iv) system studies. Moreover, a strong management team is concerned not only with the technical and financial issues arising from EUROPART, but also with information, communication and benefits for Europe

A Heterobimetallic Complex With an Unsupported Uranium(III)-Aluminum(I) Bond: (CpSiMe3)3U-AlCp* (Cp* = C5Me5)

Energy Technology Data Exchange (ETDEWEB)

Minasian, Stefan; Krinsky Ph.D., Jamin; Williams, Valerie; Arnold Ph.D., John

2008-07-23

The discovery of molecular metal-metal bonds has been of fundamental importance to the understanding of chemical bonding. For the actinides, examples of unsupported metal-metal bonds are relatively uncommon, consisting of Cp{sub 3}U-SnPh{sub 3}, and several actinide-transition metal complexes. Traditionally, bonding in the f-elements has been described as electrostatic; however, elucidating the degree of covalency is a subject of recent research. In carbon monoxide complexes of the trivalent uranium metallocenes, decreased {nu}{sub CO} values relative to free CO suggest that the U(III) atom acts as a {pi}-donor. Ephritikhine and coworkers have demonstrated that {pi}-accepting ligands can differentiate trivalent lanthanide and actinide ions, an effect that renders this chemistry of interest in the context of nuclear waste separation technology.

Radiochemical studies of neutron deficient actinide isotopes

International Nuclear Information System (INIS)

Williams, K.E.

1978-04-01

The production of neutron deficient actinide isotopes in heavy ion reactions was studied using alpha, gamma, x-ray, and spontaneous fission detection systems. A new isotope of berkelium, 242 Bk, was produced with a cross-section of approximately 10 μb in reactions of boron on uranium and nitrogen on thorium. It decays by electron capture with a half-life of 7.0 +- 1.3 minutes. The alpha-branching ratio for this isotope is less than 1% and the spontaneous fission ratio is less than 0.03%. Studies of (Heavy Ion, pxn) and (Heavy Ion, αxn) transfer reactions in comparison with (Heavy ion, xn) compound nucleus reactions revealed transfer reaction cross-sections equal to or greater than the compound nucleus yields. The data show that in some cases the yield of an isotope produced via a (H.I.,pxn) or (H.I.,αxn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z 1 + Z 2 = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,αxn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of 228 Pu, 230 Pu, 232 Cm, or 238 Cf was observed indicating that strictly empirical extrapolations of spontaneous fission half-life data is inadequate for predictions of half-lives for unknown neutron deficient actinide isotopes

Basic actinide chemistry and physics research in close cooperation with hot laboratories: ACTILAB

International Nuclear Information System (INIS)

Minato, K; Konashi, K; Fujii, T; Uehara, A; Nagasaki, S; Ohtori, N; Tokunaga, Y; Kambe, S

2010-01-01

Basic research in actinide chemistry and physics is indispensable to maintain sustainable development of innovative nuclear technology. Actinides, especially minor actinides of americium and curium, need to be handled in special facilities with containment and radiation shields. To promote and facilitate actinide research, close cooperation with the facilities and sharing of technical and scientific information must be very important and effective. A three-year-program B asic actinide chemistry and physics research in close cooperation with hot laboratories , ACTILAB, was started to form the basis of sustainable development of innovative nuclear technology. In this program, research on actinide solid-state physics, solution chemistry and solid-liquid interface chemistry is made using four main facilities in Japan in close cooperation with each other, where basic experiments with transuranium elements can be made. The 17 O-NMR measurements were performed on (Pu 0.91 Am 0.09 )O 2 to study the electronic state and the chemical behaviour of Am and Cm ions in electrolyte solutions was studied by distribution experiments.

Correlation of retention of lanthanide and actinide complexes with stability constants and their speciation

Energy Technology Data Exchange (ETDEWEB)

Datta, A.; Sivaraman, N.; Viswanathan, K.S.; Ghosh, Suddhasattwa; Srinivasan, T.G.; Vasudeva Rao, P.R. [Indira Gandhi Centre for Atomic Research, Kalpakkam (India). Chemistry Group

2013-03-01

The present study describes a correlation that is developed from retention of lanthanide and actinide complexes with the stability constant. In these studies, an ion-pairing reagent, camphor-10-sulphonic acid (CSA) was used as the modifier and organic acids such as {alpha}-hydroxy isobutyric acid ({alpha}-HIBA), mandelic acid, lactic acid and tartaric acid were used as complexing reagent for elution. From these studies, a correlation has been established between capacity factor of a metal ion, concentration of ion-pairing reagent and complexing agent with the stability constant of metal complex. Based on these studies, it has been shown that the stability constant of lanthanide and actinide complexes can be estimated using a single lanthanide calibrant. Validation of the method was carried out with the complexing agents such as {alpha}-HIBA and lactic acid. It was also demonstrated that data from a single chromatogram can be used for estimation of stability constant at various ionic strengths. These studies also demonstrated that the method can be applied for estimation of stability constant of actinides with a ligand whose value is not reported yet, e.g., ligands of importance in the lanthanide-actinide separations, chelation therapy etc. The chromatographic separation method is fast and the estimation of stability constant can be done in a very short time, which is a significant advantage especially in dealing with radioactive elements. The stability constant data was used to derive speciation data of plutonium in different oxidation states as well as that of americium with {alpha}-HIBA. The elution behavior of actinides such as Pu and Am from reversed phase chromatographic technique could be explained based on these studies. (orig.)

Spectroscopic and redox properties of curium and californium ions in concentrated aqueous carbonate-bicarbonate media

International Nuclear Information System (INIS)

Hobart, D.E.; Varlashkin, P.G.; Samhoun, K.; Haire, R.G.; Peterson, J.R.

1983-01-01

Multimilligram quantities of trivalent curium-248 and californium-249 were investigated by absorption spectroscopy, cyclic voltammetry, and bulk solution electrolysis in concentrated aqueous carbonate-bicarbonate solution. Actinide concentrations between 10 -4 and 10 -2 M were studied in 2 M sodium carbonate and 5.5 M potassium carbonate solutions at pH values from 8 to 14. The solution absorption spectra of Cm(III) and Cf(III) in carbonate media are presented for the first time and compared to literature spectra of these species in noncomplexing aqueous solution. It was anticipated that carbonate complexation of the actinide ions could provide a sufficient negative shift in the formal potentials of the M(IV)/M(III) couples of Cm and Cf to permit the generation and stabilization of their tetravalent states in aqueous carbonate-bicarbonate medium. No conclusive evidence was found in the present work to indicate the existence of any higher oxidation states of curium or californium in carbonate solution. Some possible reasons for our inability to generate and detect oxidized species of curium and californium in this medium are discussed

Advancing the scientific basis of trivalent actinide-lanthanide separations

International Nuclear Information System (INIS)

Nash, K.L.

2013-01-01

For advanced fuel cycles designed to support transmutation of transplutonium actinides, several options have been demonstrated for process-scale aqueous separations for U, Np, Pu management and for partitioning of trivalent actinides and fission product lanthanides away from other fission products. The more difficult mutual separation of Am/Cm from La-Tb remains the subject of considerable fundamental and applied research. The chemical separations literature teaches that the most productive alternatives to pursue are those based on ligand donor atoms less electronegative than O, specifically N- and S-containing complexants and chloride ion (Cl - ). These 'soft-donor' atoms have exhibited usable selectivity in their bonding interactions with trivalent actinides relative to lanthanides. In this report, selected features of soft donor reagent design, characterization and application development will be discussed. The roles of thiocyanate, aminopoly-carboxylic acids and lactate in separation processes are detailed. (authors)

4f and 5f trivalent ions complexation by diamides and uses in solvent extraction

International Nuclear Information System (INIS)

Huber, H.

1984-06-01

Extractive properties of N,N'-tetraalkylmalonamides were investigated in view to separate the actinides contained in highly radioactive wastes. N,N'-dimethyldioctylmalonamide (DMDOMA) was selected. It extracts trivalent actinide and lanthanide from concentrated nitric acid. Mineral acids extraction was studied, especially HNO 3 extraction. The distribution of HNO 3 can be interpreted by assuming that in the organic phase three main species are present: HNO 3 (DMDOMA) 2 , HNO 3 DMDOMA, (HNO 3 ) 2 DMDOMA. 5f and 4f trivalent ions are extracted according to the mechanism: M 3+ + 3NO 3 - + 4DMDOMA in equilibrium with [M(DMDOMA) 2 (NO 3 ) 3 ].(DMDOMA) 2 . The extraction of important ions like U(VI), Np(V), Pu(IV), Pu(VI), Zr(IV) and Fe(III) was investigated. The results showed that DMDOMA behave line the carbamoylmethylenephosphonates and could be an interesting alternative to these organophosphorus extractants [fr

Channeled-ion implantation of group-III and group-V ions into silicon

International Nuclear Information System (INIS)

Furuya, T.; Nishi, H.; Inada, T.; Sakurai, T.

1978-01-01

Implantation of group-III and group-V ions along [111] and [110] axes of silicon have been performed using a backscattering technique, and the depth profiles of implanted ions have been measured by the C-V method. The range of channeled Ga ions is the largest among the present data, and a p-type layer of about 6 μm is obtained by implantation at only 150 keV. The carrier profiles of channeled Al and Ga ions with deep ranges do not show any distinguishable channeled peak contrasting with the B, P, and As channeling which gives a well-defined peak. The electronic stopping cross section (S/sub e/) of channeled P ions agree well with the results of Eisen and Reddi, but in B channeling, the discrepancies of 10--20% are observed among S/sub e/ values obtained experimentally by three different groups

Removal of actinides from dilute waste waters using polymer filtration

International Nuclear Information System (INIS)

Smith, B.F.; Robison, T.W.; Gibson, R.R.

1995-01-01

More stringent US Department of Energy discharge regulations for waste waters containing radionuclides (30 pCi/L total alpha) require the development of new processes to meet the new discharge limits for actinide metal ions, particularly americium and plutonium, while minimizing waste. We have been investigating a new technology, polymer filtration, that has the potential for effectively meeting these new limits. Traditional technology uses basic iron precipitation which produces large amounts of waste sludge. The new technology is based on using water-soluble chelating polymers with ultrafiltration for physical separation. The actinide metal ions are selectively bound to the polymer and can not pass through the membrane. Small molecules and nonbinding metals pass through the membrane. Advantages of polymer filtration technology compared to ion, exchange include rapid kinetics because the binding is occurring in a homogenous solution and no mechanical strength requirement on the polymer. We will present our results on the systematic development of a new class of water-soluble chelating polymers and their binding ability from dilute acid to near neutral waters

Removal of actinides from selected nuclear fuel reprocessing wastes

International Nuclear Information System (INIS)

Navratil, J.D.; Thompson, G.H.

1979-01-01

The US Department of Energy awarded Oak Ridge National Laboratory a program to develop a cost-risk-benefit analysis of partitioning long-lived nuclides from waste and transmuting them to shorter lived or stable nuclides. Two subtasks of this program were investigated at Rocky Flats. In the first subtask, methods for solubilizing actinides in incinerator ash were tested. Two methods appear to be preferable: reaction with ceric ion in nitric acid or carbonate-nitrate fusion. The ceric-nitric acid system solubilizes 95% of the actinides in ash; this can be increased by 2 to 4% by pretreating ash with sodium hydroxide to solubilize silica. The carbonate-nitrate fusion method solubilizes greater than or equal to 98% of the actinides, but requires sodium hydroxide pretreatment. Two additional disadvantages are that it is a high-temperature process, and that it generates a lot of salt waste. The second subtask comprises removing actinides from salt wastes likely to be produced during reactor fuel fabrication and reprocessing. A preliminary feasibility study of solvent extraction methods has been completed. The use of a two-step solvent extraction system - tributyl phosphate (TBP) followed by extraction with a bidentate organophosphorous extractant (DHDECMP) - appears to be the most efficient for removing actinides from salt waste. The TBP step would remove most of the plutonium and > 99.99% of the uranium. The second step using DHDECMP would remove > 99.91% of the americium and the remaining plutonium (> 99.98%) and other actinides from the acidified salt waste. 8 figures, 11 tables

Studies of Actinides Reduction on Iron Surfaces by Means of Resonant Inelastic X-ray Scattering

International Nuclear Information System (INIS)

Kvashnina, K.O.; Butorin, S.M.; Shuh, D.K.; Ollila, K.; Soroka, I.; Guo, J.-H.; Werme, L.; Nordgren, J.

2006-01-01

The interaction of actinides with corroded iron surfaces was studied using resonant inelastic x-ray scattering (RIXS) spectroscopy at actinide 5d edges. RIXS profiles, corresponding to the f-f excitations are found to be very sensitive to the chemical states of actinides in different systems. Our results clearly indicate that U(VI) (as soluble uranyl ion) was reduced to U(IV) in the form of relatively insoluble uranium species, indicating that the iron presence significantly affects the mobility of actinides, creating reducing conditions. Also Np(V) and Pu (VI) in the ground water solution were getting reduced by the iron surface to Np(IV) and Pu (IV) respectively. Studying the reduction of actinides compounds will have an important process controlling the environmental behavior. Using RIXS we have shown that actinides, formed by radiolysis of water in the disposal canister, are likely to be reduced on the inset corrosion products and prevent release from the canister

NMR and TRLFS studies of Ln(iii) and An(iii) C5-BPP complexes.

Science.gov (United States)

Adam, Christian; Beele, Björn B; Geist, Andreas; Müllich, Udo; Kaden, Peter; Panak, Petra J

2015-02-01

C5-BPP is a highly efficient N-donor ligand for the separation of trivalent actinides, An(iii), from trivalent lanthanides, Ln(iii). The molecular origin of the selectivity of C5-BPP and many other N-donor ligands of the BTP-type is still not entirely understood. We present here the first NMR studies on C5-BPP Ln(iii) and An(iii) complexes. C5-BPP is synthesized with 10% 15 N labeling and characterized by NMR and LIFDI-MS methods. 15 N NMR spectroscopy gives a detailed insight into the bonding of C5-BPP with lanthanides and Am(iii) as a representative for trivalent actinide cations, revealing significant differences in 15 N chemical shift for coordinating nitrogen atoms compared to Ln(iii) complexes. The temperature dependence of NMR chemical shifts observed for the Am(iii) complex indicates a weak paramagnetism. This as well as the observed large chemical shift for coordinating nitrogen atoms show that metal-ligand bonding in Am(C5-BPP) 3 has a larger share of covalence than in lanthanide complexes, confirming earlier studies. The Am(C5-BPP) 3 NMR sample is furthermore spiked with Cm(iii) and characterized by time-resolved laser fluorescence spectroscopy (TRLFS), yielding important information on the speciation of trace amounts of minor complex species.

Actinide production in 136Xe bombardments of 249Cf

International Nuclear Information System (INIS)

Gregorich, K.E.

1985-08-01

The production cross sections for the actinide products from 136 Xe bombardments of 249 Cf at energies 1.02, 1.09, and 1.16 times the Coulomb barrier were determined. Fractions of the individual actinide elements were chemically separated from recoil catcher foils. The production cross sections of the actinide products were determined by measuring the radiations emitted from the nuclides within the chemical fractions. The chemical separation techniques used in this work are described in detail, and a description of the data analysis procedure is included. The actinide production cross section distributions from these 136 Xe + 249 Cf bombardments are compared with the production cross section distributions from other heavy ion bombardments of actinide targets, with emphasis on the comparison with the 136 Xe + 248 Cm reaction. A technique for modeling the final actinide cross section distributions has been developed and is presented. In this model, the initial (before deexcitation) cross section distribution with respect to the separation energy of a dinuclear complex and with respect to the Z of the target-like fragment is given by an empirical procedure. It is then assumed that the N/Z equilibration in the dinuclear complex occurs by the transfer of neutrons between the two participants in the dinuclear complex. The neutrons and the excitation energy are statistically distributed between the two fragments using a simple Fermi gas level density formalism. The resulting target-like fragment initial cross section distribution with respect to Z, N, and excitation energy is then allowed to deexcite by emission of neutrons in competition with fission. The result is a final cross section distribution with respect to Z and N for the actinide products. 68 refs., 33 figs., 6 tabs

Actinide oxide photodiode and nuclear battery

Energy Technology Data Exchange (ETDEWEB)

Sykora, Milan; Usov, Igor

2017-12-05

Photodiodes and nuclear batteries may utilize actinide oxides, such a uranium oxide. An actinide oxide photodiode may include a first actinide oxide layer and a second actinide oxide layer deposited on the first actinide oxide layer. The first actinide oxide layer may be n-doped or p-doped. The second actinide oxide layer may be p-doped when the first actinide oxide layer is n-doped, and the second actinide oxide layer may be n-doped when the first actinide oxide layer is p-doped. The first actinide oxide layer and the second actinide oxide layer may form a p/n junction therebetween. Photodiodes including actinide oxides are better light absorbers, can be used in thinner films, and are more thermally stable than silicon, germanium, and gallium arsenide.

The thermodynamic functions of gaseous actinide elements

International Nuclear Information System (INIS)

Rand, M.H.

1979-01-01

The actinide gases have large number of unobserved energy states - up to 3 x 10 6 for Pu(g) - which could contribute to the partition function and its derivatives, from which the thermal functions of these gases are calculated. Existing compilations have simply ignored these levels. By making reasonable assumptions as to the distribution of these energy states, their effect on the functions can be calculated. It is concluded that the existing compilations will be inadequate above approximately 2000K. The effect is particularly marked on the heat capacity. For example, when unobserved levels for Pu(g) are included, the heat capacity of Pu(g) reaches a maximum value of more than 12R at 3200K. Similar considerations will apply to the gaseous actinide ions. (orig.) [de

Hybrid conducting polymer materials incorporating poly-oxo-metalates for extraction of actinides; Materiaux polymeres conducteurs hybrides incorporant des polyoxometallates pour l'extraction d'actinides

Energy Technology Data Exchange (ETDEWEB)

Racimor, D

2003-09-15

The preparation and characterization of hybrid conducting polymers incorporating poly-oxo-metalates for extracting actinides is discussed. A study of the coordination of various lanthanide cations (Ce(III), Ce(IV), Nd(III)) by the mono-vacant poly-oxo-metalate {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} showed significant differences according to the cation.. Various {alpha}-A-[PW{sub 9}O{sub 34}(RPO){sub 2}]{sup 5-} hybrids were synthesized and their affinity for actinides or lanthanides was demonstrated through complexation. The first hybrid poly-oxo-metallic lanthanide complexes were then synthesized, as was the first hybrid functionalized with a pyrrole group. The electro-polymerization conditions of this pyrrole remain still to be optimized. Poly-pyrrole materials incorporating {alpha}{sub 2}-[P{sub 2}W{sub 17}O{sub 61}]{sup 10-} or its neodymium or cerium complexes as doping agents proved to be the first conducting polymer incorporating poly-oxo-metalates capable of extracting plutonium from nitric acid. (author)

Radiochemical studies of neutron deficient actinide isotopes

Energy Technology Data Exchange (ETDEWEB)

Williams, K.E.

1978-04-01

The production of neutron deficient actinide isotopes in heavy ion reactions was studied using alpha, gamma, x-ray, and spontaneous fission detection systems. A new isotope of berkelium, /sup 242/Bk, was produced with a cross-section of approximately 10 ..mu..b in reactions of boron on uranium and nitrogen on thorium. It decays by electron capture with a half-life of 7.0 +- 1.3 minutes. The alpha-branching ratio for this isotope is less than 1% and the spontaneous fission ratio is less than 0.03%. Studies of (Heavy Ion, pxn) and (Heavy Ion, ..cap alpha..xn) transfer reactions in comparison with (Heavy ion, xn) compound nucleus reactions revealed transfer reaction cross-sections equal to or greater than the compound nucleus yields. The data show that in some cases the yield of an isotope produced via a (H.I.,pxn) or (H.I.,..cap alpha..xn) reaction may be higher than its production via an xn compound nucleus reaction. These results have dire consequences for proponents of the ''Z/sub 1/ + Z/sub 2/ = Z/sub 1+2/'' philosophy. It is no longer acceptable to assume that (H.I.,pxn) and (H.I.,..cap alpha..xn) product yields are of no consequence when studying compound nucleus reactions. No evidence for spontaneous fission decay of /sup 228/Pu, /sup 230/Pu, /sup 232/Cm, or /sup 238/Cf was observed indicating that strictly empirical extrapolations of spontaneous fission half-life data is inadequate for predictions of half-lives for unknown neutron deficient actinide isotopes.

Terbium(III) ions as sensitizers of oxidation of indole and its derivatives in Fenton system

Energy Technology Data Exchange (ETDEWEB)

Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl; Staninski, Krzysztof

2017-03-15

Oxidation of indole and its derivatives in the Fenton system as a source of oxidising agents, in the presence of terbium(III) ions was studied by chemiluminescence methods to get the kinetic curves of emission decay and spectral distributions of chemiluminescence. Terbium(III) ions acted as a sensitizer of the mixtures Tb(III)-Fe(II)/Fe(III)-H{sub 2}O{sub 2}-indole or its derivative (tryptophan, tryptamine, indole-3-acetic acid and indole-3-acetyl aspartic acid). For the above indolic compounds, linear dependencies of integrated intensity of chemiluminescence on concentration of indolic compound in water and in water-acetonitrile solution were obtained. The limits of detection (LOD) and quantification (LOQ) of the indolic compounds studied were found to be by one or two orders of magnitude lower in the system with terbium(III) ions than without them. - Highlights: • Chemiluminescence emitted on oxidation of indolic compounds in Fenton system. • Tb (III) ions as sensitizers of indolic compounds oxidation in solutions. • Linear relations between CL intensity and indolic compound concentration.

Electrochemistry of carbonaceous materials; 1. Oxidation of Sardinian coal by Fe(III) ions

Energy Technology Data Exchange (ETDEWEB)

Tomat, R.; Salmaso, R.; Zecchin, S. (CNR-Instituto di Polarografia ed Elettrochimica Preparativa, Padova (Italy))

1992-04-01

Oxidation of subbitiminous coal (Sulcis basin, Sardinia, Italy) by Fe(III) ions in aqueous H{sub 2}SO{sub 4} solution was investigated over a wide temperature range (20-80{degree}C). Experimental results are in accord with a reaction scheme involving a reversible complex between coal particles and Fe(III) ions as a first step in the oxidation process. At low coal concentration, the reaction rate follows first-order kinetics in both coal and ferric ions (overall second order), while at sufficiently high coal concentration, the reaction rate is consistent with first-order kinetics in Fe(III) concentration, appearing to be independent of coal concentration. The kinetic results obtained give preliminary information on the advantageous use of the Fe(III)/slurried coal reaction system to depolarize the anodic compartment of an electrolysis cell, for the production of H{sub 2}. 11 refs., 5 figs.

Preparation and use of Cu nanoclusters as fluorescent probes to determine Au(III) ions

Energy Technology Data Exchange (ETDEWEB)

Liu, Jinshui, E-mail: jsliu@sina.com; Wang, Bin; Xu, Meijiao; Wang, Lizhen; Zhou, Zihan

2017-05-15

Polyethyleneimine-capped Cu nanoclusters (PEI-CuNCs) with a mean diameter of 2.5 nm and that emitted blue light at 485 nm were synthesized. The fluorescence of PEI-CuNCs was strongly quenched when Au(III) ions were present. Because of this specific response, a PEI-CuNC-based fluorescent turn-off sensor was developed. Under optimum conditions, a good linear relationship (R{sup 2}=0.993) was found between the relative fluorescence intensity (F{sub 0}/F) and the Au(III) ion concentration between 0.5 and 15 µM. The detection limit for Au(III) ions was 0.06 µM. The quenching mechanism was assessed by performing X-ray photoelectron spectroscopy spectra studies. The fluorescence quenching was ascribed to photo-induced electron transfer from the PEI-CuNCs to the AuCl{sub 4}{sup −} occur. Using The method described is a new way of quantifying Au(III) ions.

Heterogeneous all actinide recycling in LWR all actinide cycle closure concept

International Nuclear Information System (INIS)

Tondinelli, Luciano

1980-01-01

A project for the elimination of transuranium elements (Waste Actinides, WA) by neutron transmutation is developed in a commercial BWR with U-Pu (Fuel Actinides, FA) recycle. The project is based on the All Actinide Cycle Closure concept: 1) closure of the 'back end' of the fuel cycle, U-Pu coprocessing, 2) waste actinide disposal by neutron transmutation. The reactor core consists of Pu-island fuel assemblies containing WAs in target pins. Two parallel reprocessing lines for FAs and WAs are provided. Mass balance, hazard measure, spontaneous activity during 10 recycles are calculated. Conclusions are: the reduction in All Actinide inventory achieved by Heterogeneous All Actinide Recycling is on the order of 83% after 10 recycles. The U235 enrichment needed for a constant end of cycle reactivity decreases for increasing number of recycles after the 4th recycle. A diffusion-burnup calculation of the pin power peak factors in the fuel assembly shows that design limits can be satisfied. A strong effort should be devoted to the solution of the problems related to high values of spontaneous emission by the target pins

Actinides-1981

International Nuclear Information System (INIS)

1981-09-01

Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry

Actinides-1981

Energy Technology Data Exchange (ETDEWEB)

1981-09-01

Abstracts of 134 papers which were presented at the Actinides-1981 conference are presented. Approximately half of these papers deal with electronic structure of the actinides. Others deal with solid state chemistry, nuclear physic, thermodynamic properties, solution chemistry, and applied chemistry.

A new ion imprinted polymer based on Ru(III)-thiobarbituric acid complex for solid phase extraction of ruthenium(III) prior to its determination by ETAAS

International Nuclear Information System (INIS)

Zambrzycka, Elżbieta; Godlewska-Żyłkiewicz, Beata

2014-01-01

A new ruthenium ion imprinted polymer was prepared from the Ru(III) 2-thiobarbituric acid complex (the template), methacrylic acid or acrylamide (the functional monomers), and ethylene glycol dimethacrylate (the cross-linking agent) using 2,2′-azobisisobutyronitrile as the radical initiator. The ion imprinted polymer was characterized and used as a selective sorbent for the solid phase extraction of Ru(III) ions. The effects of type of functional monomer, sample volume, solution pH and flow rate on the extraction efficiency were studied in the dynamic mode. Ru(III) ion was quantitatively retained on the sorbents in the pH range from 3.5 to 10, and can be eluted with 4 mol L−1 aqueous ammonia. The affinity of Ru(III) for the ion imprinted polymer based on the acrylamide monomer is weaker than that for the polymer based on the methacrylic acid monomer, which therefore was used in interference studies and in analytical applications. Following extraction of Ru(III) ions with the imprint and their subsequent elution from the polymer with aqueous ammonia, Ru(III) was detected by electrothermal atomic absorption spectrometry with a detection limit of 0.21 ng mL −1 . The method was successfully applied to the determination of trace amounts of Ru(III) in water, waste, road dust and platinum ore (CRM SARM 76) with a reproducibility (expressed as RSD) below 6.4 %. (author)

Actinide immobilization in the subsurface environment by in-situ treatment with a hydrolytically unstable organophosphorus complexant: Uranyl uptake by calcium phytate

International Nuclear Information System (INIS)

Nash, K.L.; Jensen, M.P.; Schmidt, M.A.

1997-01-01

In addition to naturally occurring uranium and thorium, actinide ions exist in the subsurface environment as a result of accidental releases and intentional disposal practices associated with nuclear weapons production. These species present a significant challenge to cost-effective remediation of contaminated environments. An attractive approach to decreasing the probability of actinide migration in the subsurface is to transform the ions into a less mobile form by remote treatment. We have under development a process which relies on a polyfunctional organophosphorus complexant to sequester the mobile metal ions by complexation/cation exchange in the near term, and to subsequently decompose, transforming the actinides into insoluble phosphate mineral forms in the long term. Studies to date include identification of a suitable organophosphorus reagent, profiling of its decomposition kinetics, verification of the formation of phosphate mineral phases upon decomposition of the reagent, and extensive comparison of the actinide uptake ability of the calcium salt of the reagent as compared with hydroxyapatite. In this report, we briefly describe the process with focus on the cation exchange behavior of the calcium salt of the organophosphorus sequestrant

Recovery of actinides from TBP-Na2Co3 scrub-waste solutions: the ARALEX process

International Nuclear Information System (INIS)

Horwitz, E.P.; Bloomquist, C.A.A.; Mason, G.W.; Leonard, R.A.; Ziegler, A.A.

1979-08-01

A flowsheet for the recovery of actinides from TBP-Na 2 CO 3 scrub-waste solutions has been developed, based on batch extraction data, and tested, using laboratory-scale countercurrent extraction techniques. The process, called the ARALEX process, uses 2-ethyl-1-hexanol (2-EHOH) to extract the TBP degradation products (HDBP and H 2 MBP) from acidified Na 2 CO 3 scrub waste leaving the actinides in the aqueous phase. Dibutyl and monobutyl phosphoric acids are attached to the 2-EHOH molecules through hydrogen bonds, which also diminish the ability of the HDBP and H 2 MBP to complex actinides. Thus all actinides remain in the aqueous raffinate. Dilute sodium hydroxide solutions can be used to back-extract the dibutyl and monobutyl phosphoric acid esters as their sodium salts. The 2-EHOH can then be recycled. After extraction of the acidified carbonate waste with 2-EHOH, the actinides may be readily extracted from the raffinate with DHDECMP or, in the case of tetra- and hexavalent actinides, with TBP. The ARALEX process can also be applied to other actinide waste streams which contain appreciable concentrations of polar organic compounds (e.g., detergents) that interfere with conventional actinide ion exchange and liquid-liquid extraction procedures. 20 figures, 6 tables

U(VI) and Eu(III) ion sorption in the interface solution-phosphate solids: Structural study and mechanisms; Sorption des ions U(VI) et Eu(III) a l`interface solution - solides phosphates: Etude structurale et mechanismes

Energy Technology Data Exchange (ETDEWEB)

Drot, Romuald [Inst. de Physique Nucleaire, Paris-11 Univ., 91 - Orsay (France)

1998-09-18

As part of the storage of nuclear wastes in a deep underground disposal, radionuclides sorption on geological or engineered barriers is one of the most important factor which could enhance retardation. Thus, the knowledge of such mechanisms is needed. For this purpose, we chose to experimentally define sorption equilibria before performing simulation of retention data. Several phosphate compounds are potential candidates as engineered barrier additives. We considered Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7}, Zr{sub 2}O(PO{sub 4}){sub 2} which allow to study the effect of PO{sub 4} and P{sub 2}O{sub 7} groups separately. Eu(III) and U(IV) ions were used as structural probes in order to simulate actinides (III) and (VI) behavior. X-ray powder diffraction, IR spectroscopy and electron probe microanalysis were used to characterized the synthesized solids. Electrophoretic measurements showed an amphoteric behavior of surface sites. Moreover, laser spectro-fluorimetry experiments indicated that no diffusion phenomena of the sorbed ion inside the solid occurs. Thus, we considered that a surface complexation model should be applied. Laser spectro-fluorimetry and XPS allowed to determine the nature of surface sites. ZrP{sub 2}O{sub 7} presents only one single site (P{sub 2}O{sub 7} groups) whereas Th{sub 4}(PO{sub 4}){sub 4}P{sub 2}O{sub 7} and Zr{sub 2}O(PO{sub 4}){sub 2} admit two types of sites (PO{sub 4}/P{sub 2}O{sub 7} and PO{sub 4}/oxo groups, respectively). Sorbed species were identified using laser spectro-fluorimetry which indicate that, in KNO{sub 3} 0.5 M medium and for a known surface site, there are two surface complexes for U(VI) (sorption of UO{sup 2+}{sub 2} et de UO{sub 2}NO{sup +}{sub 3} species) and only one for Eu(III) (sorption of EuNO{sup 2+}{sub 3}). They are linked to the substrate as bidentate inner sphere complexes (EXAFS study). Surface acidity constants were determined by simulation of potentiometric titration curves obtained for each solid

Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures

International Nuclear Information System (INIS)

Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

1999-01-01

By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs

Subsurface interactions of actinide species and microorganisms : implications for the bioremediation of actinide-organic mixtures.

Energy Technology Data Exchange (ETDEWEB)

Banaszak, J.E.; Reed, D.T.; Rittmann, B.E.

1999-02-12

By reviewing how microorganisms interact with actinides in subsurface environments, we assess how bioremediation controls the fate of actinides. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. We describe how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility. We explain why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. We describe the development of mathematical models that link microbiological and geochemical reactions. Throughout, we identify the key research needs.

Separation of minor actinides from a genuine MA/LN fraction

International Nuclear Information System (INIS)

Satmark, B.; Courson, O.; Malmbeck, R.; Pagliosa, G.; Romer, K.; Glatz, J.P.

2001-01-01

Separation of the trivalent Minor Actinides (MA), Am and Cm, has been performed from a genuine MA(III) + Ln(III) solution using Bis-Triazine-Pyridine (BTP) as organic extractant. The representative MA/Ln fraction was obtained from a dissolved commercial LWR fuel (45.2 GWd/tM) submitted subsequently too a PUREX process followed by a DIAMEX process. A centrifugal extractor set-up (16-stages), working in a continuous counter-current mode, was used for the liquid-liquid separation. In the nPr-BTP process, feed decontamination factors for Am and Cm above 96 and 65, respectively were achieved. The back-extraction was more efficient for Am (99.1% recovery) than for Cm (97.5%). This experiment, using the Bis-Triazine-Pyridine molecule is the first successful demonstration of the separation of MA from lanthanides in a genuine MA/Ln fraction with a nitric acid concentration of ca. 1 M. It represents an important break through in the difficult field of minor actinide partitioning of high level liquid waste. (author)

New strategies in actinide separation - water-soluble complexing agents for the innovative SANEX process

International Nuclear Information System (INIS)

Ruff, Christian M.; Muelllich, Udo; Geist, Andreas; Panak, Petra J.

2012-01-01

Reduction of the radiotoxicity and thermal output of radioactive wastes prior to their permanent disposal is a topic of extreme interest for the issue of final nuclear waste disposal. One possibility to this end is a process referred to as actinide separation. This process can be optimised by means of a newly developed water-soluble molecule, as has been shown in studies on the molecule's complex chemistry using ultra-modern laser-based spectroscopy methods under process-relevant reaction conditions. Through the use of curium (III) and europium (III), which as members of the trivalent actinides and lanthanides family have excellent spectroscopic properties, it has been possible to generate spectroscopic and thermodynamic data which will facilitate our understanding of the complex chemistry and extraction chemistry of this molecule family.

Actinide Sciences at ITN - Basic Studies in Chemistry with Potential Interest for Partitioning, Fuel Fabrication and More

International Nuclear Information System (INIS)

Almeida, M.; Dias, M.; Goncalves, A.P.; Henriques, M.S.; Lopes, E.B.; Pereira, L.C.J.; Santos, I.C.; Verbovytskyy, Y.; Waerenborgh, J.C.; Branco, J.B.; Carretas, J.M.; Cruz, A.; Ferreira, A.C.; Gasche, T.A.; Leal, J.P.; Lopes, G.; Lourenco, C.; Marcalo, J.; Maria, L.; Monteiro, B.; Mora, E.; Pereira, C.C.L.; Paiva, I.

2010-01-01

The current activities in the area of actinide chemistry at ITN, comprising basic research studies in inorganic and organometallic chemistry, catalysis, gas-phase ion chemistry, thermochemistry, and solid state chemistry, are briefly described. Actinide (and lanthanide) chemistry studies at ITN will be pursued connecting basic research with potential applications in nuclear and non-nuclear areas. (authors)

Extraction of Lanthanide and Actinide Ions from Aqueous Mixtures Using a Carboxylic Acid-Functionalized Porous Aromatic Framework

Science.gov (United States)

2016-01-01

Porous aromatic frameworks (PAFs) incorporating a high concentration of acid functional groups possess characteristics that are promising for use in separating lanthanide and actinide metal ions, as required in the treatment of radioactive waste. These materials have been shown to be indefinitely stable to concentrated acids and bases, potentially allowing for multiple adsorption/stripping cycles. Additionally, the PAFs combine exceptional features from MOFs and inorganic/activated carbons giving rise to tunable pore surfaces and maximum chemical stability. Herein, we present a study of the adsorption of selected metal ions, Sr2+, Fe3+, Nd3+, and Am3+, from aqueous solutions employing a carbon-based porous aromatic framework, BPP-7 (Berkeley Porous Polymer-7). This material displays high metal loading capacities together with excellent adsorption selectivity for neodymium over strontium based on Langmuir adsorption isotherms and ideal adsorbed solution theory (IAST) calculations. Based in part upon X-ray absorption spectroscopy studies, the stronger adsorption of neodymium is attributed to multiple metal ion and binding site interactions resulting from the densely functionalized and highly interpenetrated structure of BPP-7. Recyclability and combustibility experiments demonstrate that multiple adsorption/stripping cycles can be completed with minimal degradation of the polymer adsorption capacity. PMID:27163056

Theoretical Studies of the Electronic Structure of the Compounds of the Actinide Elements

International Nuclear Information System (INIS)

Kaltsoyannis, Nikolas; Hay, P.J.; Li, Jun; Blaudeau, Jean-Philippe; Bursten, Bruce E.

2006-01-01

In this chapter, we will present an overview of the theoretical and computational developments that have increased our understanding of the electronic structure of actinide-containing molecules and ions. The application of modern electronic structure methodologies to actinide systems remains one of the great challenges in quantum chemistry; indeed, as will be discussed below, there is no other portion of the periodic table that leads to the confluence of complexity with respect to the calculation of ground- and excited-state energies, bonding descriptions, and molecular properties. But there is also no place in the periodic table in which effective computational modeling of electronic structure can be more useful. The difficulties in creating, isolating, and handling many of the actinide elements provide an opportunity for computational chemistry to be an unusually important partner in developing the chemistry of these elements. The importance of actinide electronic structure begins with the earliest studies of uranium chemistry and predates the discovery of quantum mechanics. The fluorescence of uranyl compounds was observed as early as 1833, a presage of the development of actinometry as a tool for measuring photochemical quantum yields. Interest in nuclear fuels has stimulated tremendous interest in understanding the properties, including electronic properties, of small actinide-containing molecules and ions, especially the oxides and halides of uranium and plutonium. The synthesis of uranocene in 1968 led to the flurry of activity in the organometallic chemistry of the actinides that continues today. Actinide organometallics (or organoactinides) are nearly always molecular systems and are often volatile, which makes them amenable to an arsenal of experimental probes of molecular and electronic structure (Marks and Fischer, 1979). Theoretical and computational studies of the electronic structure of actinide systems have developed in concert with the experimental

Quantitative description and local structures of trivalent metal ions Eu(III) and Cm(III) complexed with poly-acrylic acid

International Nuclear Information System (INIS)

Montavon, G.; Huclier-Markai, S.; Grambow, B.; Bouby, M.; Geckeis, H.; Rabung, T.; Huclier-Markai, S.; Pashalidis, I.; Amekraz, B.; Moulin, C.

2008-01-01

The trivalent metal ion (M(III) = Cm, Eu)/poly-acrylic acid (PAA) system was studied in the pH range between 3 and 5.5 for a molar PAA-to-metal ratio above 1. The interaction was studied for a wide range of PAA (0.05 mg L -1 -50 g L -1 ) and metal ion concentrations (2*10 -9 - 10 -3 M). This work aimed at 3 goals (i) to determine the stoichiometry of M(III)-PAA complexes, (ii) to determine the number of complexed species and the local environment of the metal ion, and (iii) to quantify the reaction processes. Asymmetric flow-field-flow fractionation (AsFIFFF) coupled to ICP-MS evidenced that size distributions of Eu-PAA complexes and PAA were identical, suggesting that Eu bound to only one PAA chain. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements performed with Eu and Cm showed a continuous shift of the spectra with increasing pH. The environment of complexed metal ions obviously changes with pH. Most probably, spectral variations arose from conformational changes within the M(Ill)-PAA complex due to pH variation. Complexation data describing the distribution of complexed and free metal ion were measured with Cm by TRLFS. They could be quantitatively described in the whole pH-range studied by considering the existence of only a single complexed species. This indicates that the slight changes in M(III) speciation with pH observed at the molecular level do not significantly affect the intrinsic binding constant. The interaction constant obtained from the modelling must be considered as a mean interaction constant. (authors)

Subsurface interactions of actinide species and microorganisms. Implications for the bioremediation of actinide-organic mixtures

International Nuclear Information System (INIS)

Banaszak, J.E.; Rittmann, B.E.; Reed, D.T.

1999-01-01

By reviewing how microorganisms interact with actinides in subsurface environments, the way how bioremediation controls the fate of actinides is assessed. Actinides often are co-contaminants with strong organic chelators, chlorinated solvents, and fuel hydrocarbons. Bioremediation can immobilize the actinides, biodegrade the co-contaminants, or both. Actinides at the IV oxidation state are the least soluble, and microorganisms accelerate precipitation by altering the actinide's oxidation state or its speciation. The way how microorganisms directly oxidize or reduce actinides and how microbiological reactions that biodegrade strong organic chelators, alter the pH, and consume or produce precipitating anions strongly affect actinide speciation and, therefore, mobility is described. Why inhibition caused by chemical or radiolytic toxicities uniquely affects microbial reactions is explained. Due to the complex interactions of the microbiological and chemical phenomena, mathematical modeling is an essential tool for research on and application of bioremediation involving co-contamination with actinides. Development of mathematical models that link microbiological and geochemical reactions is described. Throughout, the key research needs are identified. (author)

Actinide uptake onto zeolite-L and SAPO-34

International Nuclear Information System (INIS)

Amini, S.; Dyer, A.

1994-01-01

The characteristics of ion exchange of uranyl and americium, which are α-emitting radioactive nuclides, were examined by batch and column methods. SAPO-34 showed good selectivity for uranyl ion at pH 2-3.5, and distribution coefficients of Am 3+ and UO 2 2+ increased with equilibrium pH. γ irradiation (2 MGy) did not show any significant effect on the uptake of both of actinide ions onto L and SAPO-34. Higher doses of γ-irradiation (up to 10 MGy) created a change of equilibrium pH, and hence uptake, due to radiolysis of water and heat localization generated by γ-radiation and annealing processes. (author) 19 refs.; 15 figs.; 3 tabs

Plans for laser ablation of actinides into an ECRIS for accelerator mass spectroscopy

International Nuclear Information System (INIS)

Pardo, R.C.; Kondev, F.G.; Kondrashev, S.; Nair, C.; Palchan, T.; Rehm, E.; Scott, R.; Vondrasek, R.; Paul, M.; Collon, P.; Youinou, G.; Salvatores, M.; Palmotti, G.; McGrath, C.; Imel, G.

2012-01-01

A project using Accelerator Mass Spectrometry (AMS) at the ATLAS facility to measure neutron capture rates on a wide range of actinides in a reactor environment is underway. This project will require the measurement of many samples with high precision and accuracy. The AMS technique at ATLAS is based on production of highly-charged positive ions in an electron cyclotron resonance ion source (ECRIS) followed by linear acceleration. We have chosen to use laser ablation as the best means of feeding the actinide material into the ion source because we believe this technique will have more efficiency and lower chamber contamination thus reducing 'cross talk' between samples. In addition construction of a new multi-sample holder/changer to allow quick change between multiple samples is part of the project. The status of the project, design, and goals for initial offline ablation tests will be discussed as well as the overall project schedule. The paper is followed by the associated poster. (authors)

Effect of pKa on the extraction behavior of Am(III) in organo phosphorus acid and diglycolamide solvent system

International Nuclear Information System (INIS)

Swami, K. Rama; Antony, M.P.; Homi Bhabha National Institute, Mumbai; Kumaresan, R.; Nayak, P.K.; Venkatesan, K.A.

2018-01-01

A combination of neutral and acidic extractant has been proposed for the single-cycle separation of trivalent actinides from high-level liquid waste (HLLW). The nature of acidic extractant in the combined solvent formulation plays a profound role in deciding the extraction and stripping of trivalent actinides. Therefore, the extraction behavior of Am(III) in a solution of tetra-bis(2-ethylhexyl)-diglycolamide (TEHDGA) and acidic extractant (HA) was studied from nitric acid medium. The acidic extractants chosen were bis(2-ethylhexyl)phosphoric acid (HDEHP), bis(2-ethylhexyl)phosphonic acid (PC88A) and bis(2,4,4-trimethylpentyl)phosphinic acid (CYANEX-272) whose pKa values were 3.24, 4.51 and 6.37, respectively. The distribution ratio of Am(III) was measured as a function of various parameters such as concentration of nitric acid, TEHDGA, HA etc. The data were compared with those obtained in individual solvent systems namely 0.1 M TEHDGA/n-DD and HA/n-DD. Slope analysis of the extraction data indicated the synergic participation of both TEHDGA and HDEHP in the extraction of Am(III) at all acidities. However, antagonistic effect was observed at lower acidity when TEHDGA was mixed to PC88A or CYANEX-272 present in n-DD. Accordingly, a suitable mechanism has been proposed for the extraction of Am(III) at all acidities using these combined solvent formulation. Studies with fast reactor simulated high level liquid waste indicated that extraction of Am(III) was accompanied by co-extraction of lanthanides and unwanted metal ions such as Zr(IV), Mo(VI), Y(III) and Pd(II). However, addition of trans-1,2-diaminocyclohexane-N,N,N,N ' -tetraaceticacid (CyDTA) reduced the extraction of unwanted metal ions. Batch extraction and stripping studies indicated the possibility of using 0.1 M TEHDGA+0.25 M HDEHP in n-dodecane for the single cycle separation of Am(III) from FR-SHLLW.

Actinide colloid generation in groundwater

International Nuclear Information System (INIS)

Kim, J.I.

1990-05-01

The progress made in the investigation of actinide colloid generation in groundwaters is summarized and discussed with particular examples relevant to an understanding of the migration behaviour of actinides in natural aquifer systems. The first part deals with the characterization of colloids: groundwater colloids, actinide real-colloids and actinide pseudocolloids. The second part concentrates on the generation processes and migration behaviour of actinide pseudocolloids, which are discussed with some notable experimental examples. Importance is stressed more on the chemical aspects of the actinide colloid generation in groundwater. This work is a contribution to the CEC project MIRAGE II, particularly, to research area: complexation and colloids. (orig.)

Separation and accumulation of acitinides with the aid of a phosphoric acid polymer

International Nuclear Information System (INIS)

Novikov, A.; Geckeler, K.E.

1993-01-01

A new method for the separation and enrichment of actinides based on the use of polymer reagents is presented, in this study, poly(ethyleneimine methylphosphonic acid) was used for the interaction with actinide ions in the homogeneous phase. In conjunction with membrane filtration this reagent allows both the separation and the enrichment of actinides from dilute solutions. The retention profiles for the series of actinides U(VI), Np(V), Pu(IV), Am(III), Cm(III), Cf(III) were investigated at different pH. Retention differences between 0% and 100% were found depending on the actinide element and pH. Thus, these elements can be separated and enriched form aqueous solutions of binary or multi-component mixtures. (orig.)

The actinide beamline - A new AMS facility at ANTARES

International Nuclear Information System (INIS)

Hotchkis, M.A.C.; Lee, P.J.; Mino, N.

1998-01-01

At the ANTARES accelerator a new beamline has been commissioned, incorporating new magnetic and electrostatic analysers, to optimise the efficiency for Actinides detection by Accelerator Mass Spectrometry. The detection of Actinides, particularly the isotopic ratios of uranium and plutonium, provide unique signatures for nuclear safeguards purposes. We are currently engaged in a project to evaluate the application of AMS to the measurement of Actinides in environmental samples for nuclear safeguards. Measurement of 236 U is of particular interest as a means of tracing the anthropogenic component of uranium. 236 U is expected to be present in natural samples at an extremely low level ( 236 U: 238 U ratio ∼10 -10 ). It has recently been demonstrated that AMS has sufficient sensitivity to detect 236 U at this level. The principal components of the new beamline include: an electrostatic quadrupole, a 12 deg electrostatic deflector, a 90 deg electrostatic analyser, a multi-isotope detection system including ion counters and Faraday cups. The beamline was completed in September 1998 and initial tests have been performed with iodine samples

Rate Constants for Reactions of Radiation-Produced Transients in Aqueous Solutions of Actinides

International Nuclear Information System (INIS)

Gordon, S.; Sullivan, J.C.; Ross, A.B.

1986-01-01

Rate constants have been critically compiled for reactions of ions of the actinides Am, Cf, Cm, Np, Pu, Th, and U, as well as the element Tc, in different oxidation states with various chemical species in aqueous solution. The reactants include products of the radiolysis of water (hydrated electrons, hydrogen atoms, hydroxyl radicals, hydrogen peroxide) and transient species derived from other solutes (e.g., carbonate radical). The data are useful in the estimation of migration properties of actinides, which are relevant to waste management studies

Archetypes for actinide-specific chelating agents

International Nuclear Information System (INIS)

Smith, W.L.

1980-01-01

The complexes of uranium and thorium with monomeric hydroxamic acids can serve as archetypes for an optimized macrochelate designed for tetravalent actinides. The eight-coordinate complexes, Th(i-PrN(O)C(O)R) 4 , where R = tert-butyl or R = neopentyl, have been synthesized and their structures have been determined by x-ray diffraction. The bulky alkyl substituents impart remarkable volatility and hydrocarbon solubility to these complexes, and the steric interactions of these substituents largely determine the structures. When R = tert-butyl, the substituents occupy the corners of a tetrahedron and force the complex into a distorted cubic geometry with crystallographic S 4 symmetry. Insertion of a methylene group between the carbonyl carbon and the tert-butyl group relaxes the steric requirements, and the coordination polyhedron of the neopentyl derivative is close to the mmmm isomer of the trigonal-faced dodecahedron. Uranium tetrachloride was quantitatively oxidized via an oxygen transfer reaction with two equivalents of N-phenylbenzohydroxamic acid anion (PBHA) in tetrahydrofuran (THF) to form UO 2 Cl(PBHA)(THF) 2 and benzanilide. The structure of the uranyl complex has been determined from x-ray diffraction data; the linear uranyl ion is surrounded by a planar pentagonal array composed of two hydroxamate oxygen atoms, a chloride ion and two THF oxygens, such that the chloride ion is opposite the hydroxamate group. That the THF and phenyl rings are twisted from this equatorial plane limits the molecular geometry to that of the C 1 point group. Some aspects of the chemistry of hydroxamic acids and of their incorporation into molecules that may serve as precursors of tetravalent actinide specific sequestering agents have also been investigated

Extraction of actinides from chloride medium using pentaalkylpropanediamides

International Nuclear Information System (INIS)

Cuillerdier, C.; Musikas, C.

1991-01-01

Pyrometallurgical processes for the purification of plutonium create waste solutions containing actinides, mainly americium, in chloride medium. Studies have been undertaken to study the extraction of actinides in chloride medium (hydrochloric acid mixed with concentrated salts such as LiCl, CaCl 2 , MgCl 2 , KCl) using pentaalkylpropanediamides as extractants. Plutonium (IV) is very easily extracted, Am (III) needs a salting out agent such as LiCl. Back extraction of trivalent cations is easy in HCl <5M. Plutonium(IV) and (VI) can be stripped by reduction either with ascorbic acid or hydroxylammonium salts in weak acid medium. Several diluents can be used (aromatic, chlorinated or even aliphatic) with addition of decanol to prevent third phase formation. In conclusion diamides can be used for various wastes declassification, they are potentially completely incinerable, and, as the synthesis has been optimized, they appear to be promising extractants

Speciation analysis on Eu(3) in aqueous solution using laser-induced breakdown spectroscopy

International Nuclear Information System (INIS)

Hotokezaka, H.; Tanaka, S.; Nagasaki, S.

2001-01-01

Investigation of the chemical behaviour of lanthanides and actinides in the geosphere is important for the safety assessment of high-level radioactive waste disposal. However, determination of speciation for lanthanides and actinides is difficult, because it is too hard to distinguish between metal ion and colloidal metal in aqueous solution. Laser-induced breakdown spectroscopy (LIBS) can detect both ions and microparticles of metals in aqueous solution, especially, high sensitive to microparticles. In this study, we analysed Eu(III) ion and Eu 2 O 3 particle in aqueous solution by LIBS, and measured the hydrolysis behaviour of Eu(III) in aqueous solution. Furthermore, we tried to detect the plasma emission of Eu(III) ions sorbed on TiO 2 particles, and also tried to observe the adsorption behaviour of Eu(III) ions onto TiO 2 particles in aqueous solution. (authors)

Equilibrium constants in aqueous lanthanide and actinide chemistry from time-resolved fluorescence spectroscopy: The role of ground and excited state reactions

International Nuclear Information System (INIS)

Billard, I.; Luetzenkirchen, K.

2003-01-01

Equilibrium constants for aqueous reactions between lanthanide or actinide ions and (in-) organic ligands contain important information for various radiochemical problems, such as nuclear reprocessing or the migration of radioelements in the geosphere. We study the conditions required to determine equilibrium constants by time-resolved fluorescence spectroscopy measurements. Based on a simulation study it is shown that the possibility to determine equilibrium constants depends upon the reaction rates in the photoexcited states of the lanthanide or actinide ions. (orig.)

Gastrointestinal absorption of actinides: a review with special reference to primate data

International Nuclear Information System (INIS)

Burkart, W.

1984-01-01

Large scale geological burial of transuranic wastes from fission power production may expose segments of future generations to trace amounts of actinides in water and food, which, via gastrointestinal absorption, could result in internal doses of alpha radiation. Gastrointestinal absorption of actinide elements is a poorly understood process. Experimental studies, primarily using rodents, often produce ambiguous results with order of magnitude fluctuations in estimates of GI absorption. Since experimental conditions like the chemical form of the fed actinides or reducing and complexing capacity of the stomach content, influence the GI transfer factor in seemingly unpredictable ways, only a better understanding of events at the molecular level will enable more reliable predictions to be made of the organ burdens resulting from actinides passing through the digestive tract. From a review of the existing literature it is apparent that in vitro research data in the area of GI uptake mechanisms (i.e. transport mediated by ion carriers in body fluids and across cell membranes) are virtually non-existant. In view of the uncertainties linked to in vivo uptake experiment, models which approximate man, i.e. derived from non-human primate studies, should be the best choice of experimental systems in which to determine reliable estimates for gastrointestinal transfer factors of actinide elements. (Auth.)

STRONTIUM AND ACTINIDE SORPTION BY MST AND MMST UNDER CONDITIONS REVELANT TO THE SMALL COLUMN ION-EXCHANGE PROCESS

Energy Technology Data Exchange (ETDEWEB)

Taylor-Pashow, K.; Hobbs, D.; Poirier, M.

2011-05-06

A series of tests were performed to examine the kinetics of Sr and actinide removal by monosodium titanate (MST) and modified monosodium titanate (mMST) under mixing conditions similar to what will be provided in the Small Column Ion Exchange (SCIX) Program. Similar removal kinetics were seen for two different mixing energies, indicating that under these conditions bulk solution transport is not the rate limiting step for Sr and actinide removal. Sr removal was found to be rapid for both MST and mMST, reaching steady-state conditions within six hours. In contrast, at least six weeks is necessary to reach steady-state conditions for Pu with MST. For mMST, steady-state conditions for Pu were achieved within two weeks. The actual contact time required for the SCIX process will depend on starting sorbate concentrations as well as the requirements for the decontaminated salt solution. During testing leaks occurred in both the MST and mMST tests and evidence of potential desorption was observed. The desorption likely occurred as a result of the change in solids to liquid phase ratio that occurred due to the loss of solution. Based on these results, Savannah River National Laboratory (SRNL) recommended additional testing to further study the effect of changing phase ratios on desorption. This testing is currently in progress and results will be documented in a separate report.

Lanthanide ions (III) as sensitizers of melatonin oxidation in reaction mixtures providing reactive species of oxygen and nitrogen

Energy Technology Data Exchange (ETDEWEB)

Kaczmarek, Małgorzata, E-mail: mkaczmar@amu.edu.pl

2015-06-15

Chemiluminescence (CL) of the reactive systems providing strong oxidants (reactive species of oxygen and nitrogen) containing lanthanide ions (III) and melatonin, was studied. Kinetic curves of emission decay and spectral distributions of chemiluminescence were obtained. Analysis of differences in the intensity of chemiluminescence and CL spectra proved that excitation of Tb(III) and Dy(III) ions takes place with the energy transfer from the products of melatonin oxidation: N{sup 1}-acetyl-N{sup 2}-formyl-5-methoxykynuramine (AFMK) and N{sup 1}-acetyl-5-methoxykynuramine (AMK) to the lanthanide ions. In the system Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) a linear correlation was established between the integrated CL intensity and melatonin concent. - Highlights: • Chemiluminescence (CL) of melatonin (Mel) oxidation by reactive species of oxygen and nitrogen. • Tb(III) and Dy(III) ions as sensitizers of a melatonin oxidation process. • New CL method for determination of melatonin in pharmaceutical preparations based on CL of Fe(II)/Fe(III)–H{sub 2}O{sub 2}–Mel–Tb(III) system.

Research in actinide chemistry

International Nuclear Information System (INIS)

Choppin, G.R.

1993-01-01

This research studies the behavior of the actinide elements in aqueous solution. The high radioactivity of the transuranium actinides limits the concentrations which can be studied and, consequently, limits the experimental techniques. However, oxidation state analogs (trivalent lanthanides, tetravalent thorium, and hexavalent uranium) do not suffer from these limitations. Behavior of actinides in the environment are a major USDOE concern, whether in connection with long-term releases from a repository, releases from stored defense wastes or accidental releases in reprocessing, etc. Principal goal of our research was expand the thermodynamic data base on complexation of actinides by natural ligands (e.g., OH - , CO 3 2- , PO 4 3- , humates). The research undertakes fundamental studies of actinide complexes which can increase understanding of the environmental behavior of these elements

Actinide oxides synthesis in molten chloride. Structural studies and reaction mechanisms

International Nuclear Information System (INIS)

Vigier, J.F.

2012-01-01

Pyrochemical processes are studied as potential alternatives to hydrochemical processes for spent nuclear fuel treatment. The CEA pyrochemical process led to a molten LiCl-CaCl 2 (30-70% mol) salt at 700 C with solubilized actinides at the oxidation state (III). The study developed in this thesis concerns actinide oxides synthesis in this media for nuclear fuel re-fabrication. This synthesis was done by wet argon sparging. First, this conversion method is described for neodymium (III) and cerium (III) co-conversion. The conversion rates are around 99.9%. The obtained powders contain mixed oxychloride Ce 1-x Nd x OCl as main component, with a small amount of mixed oxide Ce 1-x Nd x O 2-0,5x for the high cerium ratio. A second oxychloride CeIV(Nd 0.7 Ce 0.3 ) III O 3 Cl is obtained in specific conditions and in very low quantity. The structure of this oxychloride is described in this study. The partially oxidative property of the conversion method induces the oxidation of a part of cerium (III) to oxidation state (IV). In the case of uranium (III) conversion by wet argon sparging, all the uranium is oxidized and give the oxide UO 2 as single compound. The conversion rate for this element is over 99.9% in the molten chloride, but significant amount of uranium is lost by volatilization during the conversion. The study shows the oxygen sensitivity of uranium during the conversion, inducing oxidation over the oxidation state (IV), and giving UO 2+x or uranate CaUO 4 . As a consequence, oxygen led to calcium pollution in the precipitate. Finally, the U(III) and Pu(III) co-conversion study shows the highest precipitation sensitivity of uranium (III) in comparison with plutonium (III), responsible of a successive conversion of the two elements, giving an oxide mixture of UO 2 et PuO 2 with quantitative conversion rate. Surprisingly, the conversion of Pu(III) in the same conditions led to a mixture of PuO 2 and PuOCl, characteristic of a partial oxidation from Pu (III) to Pu

Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

Energy Technology Data Exchange (ETDEWEB)

Cassayre, L., E-mail: cassayre@chimie.ups-tlse.fr [Laboratoire de Genie Chimique (LGC), Departement Procedes Electrochimiques, CNRS-UMR 5503, Universite de Toulouse III - Paul Sabatier, 31062 Toulouse (France); Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P. [European Commission, JRC, Institute for Transuranium Elements, Postfach 2340, 76125 Karlsruhe (Germany)

2011-07-01

Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl{sub 3}. A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl{sub 3} alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl{sub 2}/UAl{sub 3} molar ratio, providing complete chlorination of the alloy without formation of volatile UCl{sub 5} and UCl{sub 6}. The results showed high efficient chlorination at a temperature of 150 deg. C.

Recovery of actinides from actinide-aluminium alloys by chlorination: Part I

International Nuclear Information System (INIS)

Cassayre, L.; Soucek, P.; Mendes, E.; Malmbeck, R.; Nourry, C.; Eloirdi, R.; Glatz, J.-P.

2011-01-01

Pyrochemical processes in molten LiCl-KCl are being developed in ITU for recovery of actinides from spent nuclear fuel. The fuel is anodically dissolved to the molten salt electrolyte and actinides are electrochemically reduced on solid aluminium cathodes forming solid actinide-aluminium alloys. A chlorination route is being investigated for recovery of actinides from the alloys. This route consists in three steps: Vacuum distillation for removal of the salt adhered on the electrode, chlorination of the actinide-aluminium alloys by chlorine gas and sublimation of the formed AlCl 3 . A thermochemical study showed thermodynamic feasibility of all three steps. On the basis of the conditions identified by the calculations, experiments using pure UAl 3 alloy were carried out to evaluate and optimise the chlorination step. The work was focused on determination of the optimal temperature and Cl 2 /UAl 3 molar ratio, providing complete chlorination of the alloy without formation of volatile UCl 5 and UCl 6 . The results showed high efficient chlorination at a temperature of 150 deg. C.

Heavy ion induced damage in MgAl sub 2 O sub 4 , an inert matrix candidate for the transmutation of minor actinides

CERN Document Server

Wiss, T

1999-01-01

Magnesium aluminum spinel (MgAl sub 2 O sub 4) is a material selected as a possible matrix for transmutation of minor actinides by neutron capture or fission in nuclear reactors. To study the radiation stability of this inert matrix, especially against fission product impact, irradiations with heavy energetic ions or clusters have been performed. The high electronic energy losses of the heavy ions in this material led to the formation of visible tracks as evidenced by transmission electron microscopy for 30 MeV C sub 6 sub 0 -Buckminster fullerenes and for ions of energy close to or higher than fission energy ( sup 2 sup 0 sup 9 Bi with 120 MeV and 2.38 GeV energy). The irradiations at high energies showed a pronounced degradation of the spinel. Additionally, MgAl sub 2 O sub 4 exhibited a large swelling for irradiation at high fluences with fission products of fission energy (here I-ions of 72 MeV) and at temperatures <= 500 deg. C. These observations are discussed from the technological point of view in ...

The study of Cr(III) complexation in the xylem sap using ion exchange and radiotracer

International Nuclear Information System (INIS)

Juneja, Shikha; Prakash, Satya

2003-01-01

Radiotracer was employed to carry out ion exchange experiments to study the chromium speciation in the in vitro samples of xylem sap of maize stem of 60 days old plants. Cr(III) radiolabelled with its radioactive isotope ( 51 Cr) was mixed with both the ion exchange fraction of the sap which represented the carboxylic acids, as well as the whole sap and was analysed for complexation after 10 and 30 days at 25 degC. Prior to this, the ion exchange elution chromatography of Cr(III), and the Cr(III) complexes with oxalic and citric acid were used to compare the complexes being formed in the in vitro studies. The in vitro Cr(III) complexation results indicated that Cr(III) was vitally present as anionic species. The elution curve trend was similar to that of citric acid complexation. Citric acid was also found to be the major complexing acid in the xylem sap as determined by HPLC. The results indicate the transportation of Cr(III) as a citrate complex in the xylem sap of maize plants. (author)

Leaching of irradiated polymers: solution characterization and actinides complexation

International Nuclear Information System (INIS)

Fromentin, Elodie

2017-01-01

The first aim of this work is to study the degradation of an industrial poly-esterurethane (PURm) by radio-oxidation and then by leaching in an alkaline aqueous solution. The second aim is to measure the complexing power of hydro-soluble degradation products (HDP) with actinides. To reach these goals, PURm was first characterized and then radio-oxidized at room temperature with γ rays up to 10 MGy. Second, it was leached at pH 13.3 at different temperature values. Numerous analytical techniques were employed in order to characterize the HDP which were obtained. Europium(III) was used as an analogue of actinides(III) and the behavior of HDP with europium(III) was analyzed by time-resolved luminescence spectroscopy (TRLS). Whatever the dose received by PURm, adipic acid and butane-1,4-diol are the two main HDP in leachates. The leaching data acquired at 40 and 60 C, on the 1 MGy radio-oxidized PURm, correlate with the model given by Yoon et al. (1997). However, the data at room temperature (22 C in average) are not in agreement with the model. Nevertheless, it seems that the plateau which was reached at long-term leaching is the same whatever the temperature used in this study. The results allow to conclude that the predominant mechanism occurring during the leaching of unirradiated and radio-oxidized PURm in an alkaline medium is the hydrolysis of the soft segments ester groups. The complexation of europium(III) by HDP in alkaline medium was demonstrated. The measurement of the complexing power and the identification of ligands was achieved under certain conditions. (author) [fr

A Thermodynamic Model for Acetate and Lactate Complexation with Am(III), Th(IV), Np(V)and U(V I) Valid to High Ionic Strength

International Nuclear Information System (INIS)

Moore, C.R.; Free, S.J.; Bynum, R.V.

1999-01-01

The organic ligands acetate, lactate, oxalate and EDTA have been identified as components of wastes targeted for disposal in the Waste Isolation Pilot Plant (WIPP) located in Southeastern New Mexico. The presence of these ligands may increase dissolved actinide concentrations and impact chemical radiation during transport. The current work considers the complexation of Am(III), Th (IV) , Np(V), and U(V I) with two of the organic ligands, acetate and lactate, in Na CI media from dilute through high concentration. A thermodynamic model for actinide complexation with the organic ligands has been developed based on the Pitzer activity coefficient formalism and the Harvie-Moller-Weare, Felmy-Weare database for describing brine evaporites systems. The model was parameterized using first apparent stability constant data from the literature. Because of complexation of other metal ions (Fe, Mg, Ni, Pb, etc.) present in the WIPP disposal room with the organic ligands, preliminary results from model calculations indicate the organic ligands do not significantly increase dissolved actinide concentrations

New strategy for minor actinides partitioning preliminary results on the electrovolatilization of ruthenium and on the stabilization of Am(IV) in nitric acid with phosphotunsgstate ligand

International Nuclear Information System (INIS)

Adnet, J.M.; Madic, C.

1989-01-01

On problems related to the long term storage in deep geological repositories of high active wastes (H.A.W.) is due to the presence of minor actinide isotopes. Thus after the decay of the fission products (≅ 300 years) the toxicity of these H.A.W. is mainly due to the minor actinides. One solution is based on actinide partitioning followed by transmutation into fission products with short half-lives. A simpler processes than those developed previously, can be based on the possible oxidation of minor actinides to the + IV or + VI oxidation states and their selective extraction. The first step to study is the elimination of the ruthenium (whose presence would be detrimental to oxidize minor actinides) which can be done by electrovolatilization of Ru on the RuO 4 form. The rate of electrovolatilization can be increased by the use of the following electronic mediators, AgI/AgII(1); CeIII/Ce(2), and CoII/CoIII(3), the efficiency of which decreases in the order: 1 > 2 > 3. The effectiveness of that process has been proven when treating real H.A.W solution produced during the study of the reprocessing of a MOX fuel irradiated to as burn-up of 52 GWd/t in a LWR: complete Ru removal was obtained. The second part of the study concerns the electrochemical oxidation of AmIII in nitric acid solutions in the presence of a strong complexing agent: P 2 W 17 O 61 K 10 (P.W.).Total americium oxidation to AmIV can be obtained in nitric acid solution with a concentration up to 8 M. No particular drawback was induced by the presence of an amount of lanthanide III (NdIII) in 6 fold excess vs P.W. The stability of AmIV was studied. The other actinides will be present in these solutions, after the electrochemical oxidation step, in the + VI or+ IV oxidation states, thus a selective extraction (vs fission products) could be performed. A possible way to extract actinide IV/P.W complexes is to use dodecylamine nitrate as extractant

Broad-beam, high current, metal ion implantation facility

International Nuclear Information System (INIS)

Brown, I.G.; Dickinson, M.R.; Galvin, J.E.; Godechot, X.; MacGill, R.A.

1990-07-01

We have developed a high current metal ion implantation facility with which high current beams of virtually all the solid metals of the Periodic Table can be produced. The facility makes use of a metal vapor vacuum arc ion source which is operated in a pulsed mode, with pulse width 0.25 ms and repetition rate up to 100 pps. Beam extraction voltage is up to 100 kV, corresponding to an ion energy of up to several hundred keV because of the ion charge state multiplicity; beam current is up to several Amperes peak and around 10 mA time averaged delivered onto target. Implantation is done in a broad-beam mode, with a direct line-of-sight from ion source to target. Here we describe the facility and some of the implants that have been carried out using it, including the 'seeding' of silicon wafers prior to CVD with titanium, palladium or tungsten, the formation of buried iridium silicide layers, and actinide (uranium and thorium) doping of III-V compounds. 16 refs., 6 figs

Actinides

International Nuclear Information System (INIS)

Martinot, L.; Fuger, J.

1985-01-01

The oxidation behavior of the actinides is explained on the basis of their electronic structure. The actinide elements, actinium, thorium, protactinium, uranium, neptunium, plutonium, americium, curium, berkelium, californium, einsteinium, fermium, mendelevium, nobelium, and laurencium are included. For all except the last three elements, the points of discussion are oxidation states, Gibbs energies and potentials, and potential diagram for the element in acid solution; and thermodynamic properties of these same elements are tabulated. References are cited following discussion of each element with a total of 97 references being cited. 13 tables

A review of the demonstration of innovative solvent extraction processes for the recovery of trivalent minor actinides from PUREX raffinate

International Nuclear Information System (INIS)

Modolo, G.; Wilden, A.; Geist, A.; Magnusson, D.; Malmbeck, R.

2012-01-01

The selective partitioning (P) of long-lived minor actinides from highly active waste solutions and their transmutation (T) to short-lived or stable isotopes by nuclear reactions will reduce the long-term hazard of the high-level waste and significantly shorten the time needed to ensure their safe confinement in a repository. The present paper summarizes the on-going research activities at Forschungszentrum Juelich (FZJ), Karlsruher Institut fuer Technologie (KIT) and Institute for Transuranium Elements (ITU) in the field of actinide partitioning using innovative solvent extraction processes. European research over the last few decades, i.e. in the NEWPART, PARTNEW and EUROPART programmes, has resulted in the development of multi-cycle processes for minor actinide partitioning. These multi-cycle processes are based on the co-separation of trivalent actinides and lanthanides (e.g. by the DIAMEX process), followed by the subsequent actinide(III)/lanthanide(III) group separation in the SANEX process. The current direction of research for the development of innovative processes within the recent European ACSEPT project is discussed additionally. This paper is focused on the development of flow-sheets for recovery of americium and curium from highly active waste solutions. The flow-sheets are verified by demonstration processes, in centrifugal contactors, using synthetic or genuine fuel solutions. The feasibility of the processes is also discussed. (orig.)

Uptake of Au(III) Ions by Aluminum Hydroxide and Their Spontaneous Reduction to Elemental Gold (Au(0)).

Science.gov (United States)

Yokoyama; Matsukado; Uchida; Motomura; Watanabe; Izawa

2001-01-01

The behavior of AuCl(4)(-) ions during the formation of aluminum hydroxide at pH 6 was examined. With an increase in NaCl concentration, the content of gold taken up by aluminum hydroxide decreased, suggesting that chloro-hydroxy complexes of Au(III) ion were taken up due to the formation of Al-O-Au bonds. It was found unexpectedly that the Au(III) ions taken up were spontaneously reduced to elemental gold without addition of a specific reducing reagent and then colloidal gold particles were formed. The mechanisms for the uptake of Au(III) ions by aluminum hydroxide and for their spontaneous reduction are discussed. Copyright 2001 Academic Press.

Structural study of the uranyl and rare earth complexation functionalized by the CMPO; Etude structurale de la complexation de l'uranyle et des ions lanthanides par des calixarenes fonctionnalises par le CMPO

Energy Technology Data Exchange (ETDEWEB)

Cherfa, S

1998-12-10

In view of reducing the volume of nuclear waste solutions, a possible way is to extract simultaneously actinide and lanthanide ions prior to their ulterior separation.. Historically, the two extractant families used for nuclear waste reprocessing are the phosphine oxides and the CMPO (Carbamoyl Methyl Phosphine Oxide). For a better understanding of the complexes formed during extraction, we undertook structural studies of the complexes formed between uranyl and lanthanide (III) ions and the two classes of ligands cited above. These studies have been performed by X-ray diffraction on single crystals. Recently, a new type of extractants of lanthanide (III) and actinide (III) ions has been developed. When the Organic macrocycle called calixarene (an oligomeric compound resulting from the poly-condensation of phenolic units) is functionalized by a CMPO ligand, the extracting power, in terms of yield and selectivity towards lightest lanthanides, is greatly enhanced compared to the one measured for the single CMPO. Our X-ray diffraction studies allowed us to characterise, in terms of stoichiometry and monodentate or bidentate coordination mode of the CMPO functions, the complexes of calix[4]arene-CMPO (with four phenolic units) with lanthanide nitrates and uranyl. These different steps of characterisation enabled us to determine the correlation between the structures of the complexes and both selectivity and exacerbation of the extracting power measured in the liquid phase. (author)

Theoretical and experimental study of actinide complexes with monoamides and organophosphorus ligands in solution

International Nuclear Information System (INIS)

Ribokaite, Kristina

2013-01-01

Monoamides and organophosphate are of great interest for the nuclear fuel cycle. Such ligands can selectively extract actinides in liquid-liquid extraction processes. The structure of the extractant (its functional group and its alkyl substituents) has a predominant role in the selective separation of actinides. This thesis concerns the theoretical and experimental studies of model systems in the aim of better understanding of the effect on molecular structures of the complexes. Structures of actinides complexes formed with model ligands in simple media (water or methanol in the presence of nitrate ions) have been characterized. At first, the complexation of uranyl by monoamide and phosphine oxide was studied in water and methanol. Molecular Dynamics simulations and DFT calculations were used to quantify the stability of uranyl complexes with those ligands, and to determine their structural properties. The theoretical results were then compared with experimental results obtained by UV-visible, infrared, Raman and EXAFS on the same chemical systems. The results were used to highlight the greater stability of uranyl complexes with phosphine oxide and monoamides. Further spectroscopic measurements combined with molecular modeling were used to gain a better understanding of the coordination mode of nitrate ion around the uranyl in both water and methanol. Finally, DFT calculations were used to study the influence of the structure of the monoamide or organophosphorus ligand and their interaction with the actinides (IV, VI) including steric effects in the first coordination sphere. (author) [fr

High-performance separation and supercritical extraction of lanthanides and actinides

International Nuclear Information System (INIS)

Datta, Arpita; Sujatha, K.; Kumar, R.; Sivaraman, N.; Srinivasan, T.G.; Vasudeva Rao, P.R.

2010-01-01

Extensive studies were carried out at Chemistry Group, IGCAR for the rapid separation of individual lanthanides and actinides using dynamic ion-exchange chromatographic technique. The atom percent fission was determined from the concentrations of the lanthanide fission products, uranium and plutonium contents of dissolver solution. These advantages were exploited to significantly reduce analysis time, liquid waste generation as well as dose to operator. Supercritical fluid extraction (SFE) of actinides from waste matrices was studied in detail at our laboratory using modified supercritical carbon dioxide (Sc-CO 2 ). Complete extraction and recovery of uranium, plutonium and americium from various matrices was achieved using Sc-CO 2 modified with suitable ligands. The technique was demonstrated for the recovery of plutonium from actual waste received from different laboratories. (author)

Intramolecular deactivation processes of electronically excited Lanthanide(III) complexes with organic acids of low molecular weight

Science.gov (United States)

Burek, Katja; Eidner, Sascha; Kuke, Stefanie; Kumke, Michael U.

2018-02-01

The luminescence of Lanthanide(III) complexes with different model ligands was studied under direct as well as sensitized excitation conditions. The research was performed in the context of studies dealing with deep-underground storages for high-level nuclear waste. Here, Lanthanide(III) ions served as natural analogues for Actinide(III) ions and the low-molecular weight organic ligands are present in clay minerals and furthermore, they were employed as proxies for building blocks of humic substances, which are important complexing molecules in the natural environment, e.g., in the far field of a repository site. Time-resolved luminescence spectroscopy was applied for a detailed characterization of Eu(III), Tb(III), Sm(III) and Dy(III) complexes in aqueous solutions. Based on the observed luminescence the ligands were tentatively divided into two groups (A, B). The luminescence of Lanthanide(III) complexes of group A was mainly influenced by an energy transfer to OH-vibrations. Lanthanide(III) complexes of group B showed ligand-related luminescence quenching, which was further investigated. To gain more information on the underlying quenching processes of group A and B ligands, measurements at different temperatures (77 K ≤ T ≤ 353 K) were performed and activation energies were determined based on an Arrhenius analysis. Moreover, the influence of the ionic strength between 0 M ≤ I ≤ 4 M on the Lanthanide(III) luminescence was monitored for different complexes, in order to evaluate the influence of specific conditions encountered in host rocks foreseen as potential repository sites.

Speciation of actinides in aqueous solution by time-resolved laser-induced fluorescence spectroscopy (TRLFS)

International Nuclear Information System (INIS)

Kimura, Takaumi; Kato, Yoshiharu; Meinrath, G.; Yoshida, Zenko; Choppin, G.R.

1995-01-01

Time-resolved laser-induced fluorescence spectroscopy (TRLFS) as a sensitive and selective method has been applied to the speciation of actinides in aqueous solution. Studies on hydrolysis and carbonate complexation of U(VI) and on determination of hydration number of Cm(III) are reported. (author)

Europium (III) and americium (III) stability constants with humic acid

International Nuclear Information System (INIS)

Torres, R.A.; Choppin, G.R.

1984-01-01

The stability constants for tracer concentrations of Eu(III) and Am(III) complexes with a humic acid extracted from a lake-bottom sediment were measured using a solvent extraction system. The organic extractant was di(2-ethylhexyl)-phosphoric acid in toluene while the humate aqueous phase had a constant ionic strength of 0.1 M (NaClO 4 ). Aqueous humic acid concentrations were monitored by measuring uv-visible absorbances at approx.= 380 nm. The total carboxylate capacity of the humic acid was determined by direct potentiometric titration to be 3.86 +- 0.03 meq/g. The humic acid displayed typical characteristics of a polyelectrolyte - the apparent pKsub(a), as well as the calculated metal ion stability constants increased as the degree of ionization (α) increased. The binding data required a fit of two stability constants, β 1 and β 2 , such that for Eu, log β 1 = 8.86 α + 4.39, log β 2 = 3.55 α + 11.06 while for Am, log β 1 = 10.58 α + 3.84, log β 2 = 5.32 α + 10.42. With hydroxide, carbonate, and humate as competing ligands, the humate complex associated with the β 1 constant is calculated to be the dominant species for the trivalent actinides and lanthanides under conditions present in natural waters. (orig.)

Actinide recycle

Energy Technology Data Exchange (ETDEWEB)

Till, C; Chang, Y [Argonne National Laboratory, Argonne, IL (United States)

1990-07-01

A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository.

Actinide recycle

International Nuclear Information System (INIS)

Till, C.; Chang, Y.

1990-01-01

A multitude of studies and assessments of actinide partitioning and transmutation were carried out in the late 1970s and early 1980s. Probably the most comprehensive of these was a study coordinated by Oak Ridge National Laboratory. The conclusions of this study were that only rather weak economic and safety incentives existed for partitioning and transmuting the actinides for waste management purposes, due to the facts that (1) partitioning processes were complicated and expensive, and (2) the geologic repository was assumed to contain actinides for hundreds of thousands of years. Much has changed in the few years since then. A variety of developments now combine to warrant a renewed assessment of the actinide recycle. First of all, it has become increasingly difficult to provide to all parties the necessary assurance that the repository will contain essentially all radioactive materials until they have decayed. Assurance can almost certainly be provided to regulatory agencies by sound technical arguments, but it is difficult to convince the general public that the behavior of wastes stored in the ground can be modeled and predicted for even a few thousand years. From this point of view alone there would seem to be a clear benefit in reducing the long-term toxicity of the high-level wastes placed in the repository

Monazite-type ceramics for conditioning of minor actinides. Structural characterization and properties

International Nuclear Information System (INIS)

Babelot, Carole

2013-01-01

damage created by the recoils accompanying alpha-decay can be simulated on ceramic matrices. Preliminary experiments are realized by means of ion bombardment. Kr 2+ ions are implanted in La-monazite-type pellets, and the effects on the LaPO 4 structure resulting from the Raman spectroscopy are poor. On a laboratory scale, the promising characteristics of the monazite mineral are found again in the synthetic phosphate. In particular, the doping of actinide surrogates is successful and the corrosion tests under repository conditions show a good resistance of the samples. The results achieved in this work confirm that among other favorable ceramics (e.g. pyrochlore) the ''monazite-route'' has to be further pursued regarding the research on the conditioning of MA.

Phosphonates as alternative to tributyl phosphate for the separation of actinides from fission products

International Nuclear Information System (INIS)

Vyas, Chirag K.; Joshirao, Pranav M.; Manchanda, Vijay K.; Rao, C.V.S. Brahmmananda; Jayalakshmi, S.

2015-01-01

The present work investigates the role of increase in the basicity of organophosphorus extractant (dialkylalkyl phosphonates) on the uptake of actinides and fission products vis-a-vis tributyl phosphate (TBP), currently employed as a universal extractant. Two dialkylalkyl phosphonates viz. dibutylpropyl phosphonate (DBPrP) and dibutylpentyl phosphonate (DBPeP) were synthesized, characterized and evaluated for their solvent extraction behavior towards U(VI), Th(IV), Eu(III) and Tc(VII) in nitric acid medium ranging from 0.01-6 M. It was observed that increasing the basicity of the phosphoryl oxygen enhanced the uptake of the actinides and the distribution coefficient values were significantly larger as compared to TBP. The limiting organic concentration (LOC) value was estimated for Th(IV) for these extractants and compared with the TBP system. The separation factors of actinides with phosphonates over Tc(VII) are distinctly better than that with TBP.

Galvanic reduction of uranium(III) chloride from LiCl-KCl eutectic salt using gadolinium metal

Science.gov (United States)

Bagri, Prashant; Zhang, Chao; Simpson, Michael F.

2017-09-01

The drawdown of actinides is an important unit operation to enable the recycling of electrorefiner salt and minimization of waste. A new method for the drawdown of actinide chlorides from LiCl-KCl molten salt has been demonstrated here. Using the galvanic interaction between the Gd/Gd(III) and U/U(III) redox reactions, it is shown that UCl3 concentration in eutectic LiCl-KCl can be reduced from 8.06 wt.% (1.39 mol %) to 0.72 wt.% (0.12 mol %) in about an hour via plating U metal onto a steel basket. This is a simple process for returning actinides to the electrorefiner and minimizing their loss to the salt waste stream.

Neodymium partitioning in zirconolite-based glass-ceramics designed for minor actinides immobilization

International Nuclear Information System (INIS)

Loiseau, P.; Caurant, D.; Baffier, N.; Fillet, C.

2000-01-01

This study deals with glass-ceramic matrices designed for the conditioning of minor actinides, in which zirconolite crystals (CaZrTi 2 O 7 ) are homogeneously dispersed in a residual glassy matrix. Good immobilization performances require a high enrichment of actinides in the crystalline phase (double containment principle). Glass-ceramics are obtained by controlled devitrification of an aluminosilicate parent glass containing large amounts of TiO 2 and ZrO 2 . Neodymium was selected to simulate the trivalent minor actinides. Crystallization was performed at 1200 deg. C for various Nd 2 O 3 contents (0 - 10 wt. %). In all cases, zirconolite crystallization is obtained in the bulk of glass-ceramics. The evolution of Nd 3+ location between the crystals and the residual glass was followed by electron spin resonance and optical absorption. Both techniques demonstrate that neodymium is partly incorporated in zirconolite crystals. Moreover, total Nd 2 O 3 content in parent glass has a strong effect on Nd 3+ ions distribution. (authors)

Recent development in computational actinide chemistry

International Nuclear Information System (INIS)

Li Jun

2008-01-01

Ever since the Manhattan project in World War II, actinide chemistry has been essential for nuclear science and technology. Yet scientists still seek the ability to interpret and predict chemical and physical properties of actinide compounds and materials using first-principle theory and computational modeling. Actinide compounds are challenging to computational chemistry because of their complicated electron correlation effects and relativistic effects, including spin-orbit coupling effects. There have been significant developments in theoretical studies on actinide compounds in the past several years. The theoretical capabilities coupled with new experimental characterization techniques now offer a powerful combination for unraveling the complexities of actinide chemistry. In this talk, we will provide an overview of our own research in this field, with particular emphasis on applications of relativistic density functional and ab initio quantum chemical methods to the geometries, electronic structures, spectroscopy and excited-state properties of small actinide molecules such as CUO and UO 2 and some large actinide compounds relevant to separation and environment science. The performance of various density functional approaches and wavefunction theory-based electron correlation methods will be compared. The results of computational modeling on the vibrational, electronic, and NMR spectra of actinide compounds will be briefly discussed as well [1-4]. We will show that progress in relativistic quantum chemistry, computer hardware and computational chemistry software has enabled computational actinide chemistry to emerge as a powerful and predictive tool for research in actinide chemistry. (authors)

An Advanced TALSPEAK Concept for Separating Minor Actinides. Part 1. Process Optimization and Flowsheet Development

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Levitskaia, Tatiana G. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Wilden, Andreas [Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany; Casella, Amanda J. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Hall, Gabriel B. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Lin, Leigh [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Sinkov, Sergey I. [Pacific Northwest National Laboratory, Nuclear Science and Engineering Group, Richland, WA, USA; Law, Jack D. [Idaho National Laboratory, Aqueous Separations and Radiochemistry Department, Idaho Falls, ID, USA; Modolo, Giuseppe [Forschungszentrum Jülich GmbH, Institut für Energie- und Klimaforschung – Nukleare Entsorgung und Reaktorsicherheit (IEK-6), Jülich, Germany

2017-08-18

A system is being developed to separate trivalent actinides from lanthanide fission product elements that uses 2-ethylhexylphosphonic acid mono-2-ethylhexyl ester to extract the lanthanide ions into an organic phase, while the actinide ions are held in the citrate-buffered aqueous phase by complexation to N-(2-hydroxyethyl)ethylenediamine-N,N',N'-triacetic acid (HEDTA). Earlier investigations of this system using a 2-cm centrifugal contactor revealed that the relatively slow extraction of Sm3+, Eu3+, and Gd3+ resulted in low separation factors from Am3+. In the work reported here, adjustments to the aqueous phase chemistry were made to improve the extraction rates. The results suggest that increasing the concentration of the citric acid buffer from 0.2 to 0.6 mol/L, and lowering the pH from 3.1 to 2.6, significantly improved lanthanide extraction rates resulting in an actinide/lanthanide separation system suitable for deployment in centrifugal contactors. Experiments performed to evaluate whether the lanthanide extraction rates can be improved by replacing aqueous HEDTA with nitrilotriacetic acid (NTA) exhibited promising results. However, NTA exhibited an unsatisfactorily high distribution value for Am3+ under the extraction conditions examined.

Actinide isotopic analysis systems

International Nuclear Information System (INIS)

Koenig, Z.M.; Ruhter, W.D.; Gunnink, R.

1990-01-01

This manual provides instructions and procedures for using the Lawrence Livermore National Laboratory's two-detector actinide isotope analysis system to measure plutonium samples with other possible actinides (including uranium, americium, and neptunium) by gamma-ray spectrometry. The computer program that controls the system and analyzes the gamma-ray spectral data is driven by a menu of one-, two-, or three-letter options chosen by the operator. Provided in this manual are descriptions of these options and their functions, plus detailed instructions (operator dialog) for choosing among the options. Also provided are general instructions for calibrating the actinide isotropic analysis system and for monitoring its performance. The inventory measurement of a sample's total plutonium and other actinides content is determined by two nondestructive measurements. One is a calorimetry measurement of the sample's heat or power output, and the other is a gamma-ray spectrometry measurement of its relative isotopic abundances. The isotopic measurements needed to interpret the observed calorimetric power measurement are the relative abundances of various plutonium and uranium isotopes and americium-241. The actinide analysis system carries out these measurements. 8 figs

Spectroscopic investigation of complexation of Cm(III) und Eu(III) with partitioning-relevant N-donor ligands

International Nuclear Information System (INIS)

Bremer, Antje

2014-01-01

The separation of trivalent actinides and lanthanides is an essential part of the development of improved nuclear fuel cycles. Liquid-liquid extraction is an applicable technique to achieve this separation. Due to the chemical similarity and the almost identical ionic radii of trivalent actinides and lanthanides this separation is, however, only feasible with highly selective extracting agents. It has been proven that molecules with soft sulphur or nitrogen donor atoms have a higher affinity for trivalent actinides. In the present work, the complexation of Cm(III) and Eu(III) with N-donor ligands relevant for partitioning has been studied by time-resolved laser fluorescence spectroscopy (TRLFS). This work aims at a better understanding of the molecular reason of the selectivity of these ligands. In this context, enormous effort has been and is still put into detailed investigations on BTP and BTBP ligands, which are the most successful N-donor ligands for the selective extraction of trivalent actinides, to date. Additionally, the complexation and extraction behavior of molecules which are structurally related to these ligands is studied. The ligand C5-BPP (2,6-bis(5-(2,2-dimethylpropyl)-1H-pyrazol-3-yl)pyridine) where the triazine rings of the aromatic backbone of the BTP ligands have been replaced by pyrazole rings is one of these molecules. Laser fluorescence spectroscopic investigation of the complexation of Cm(III) with this ligand revealed stepwise formation of three (Cm(C5-BPP) n ) 3+ complexes (n = 1 - 3). The stability constant of the 1:3 complex was determined (log β 3 = 14.8 ± 0.4). Extraction experiments have shown that, in contrast to BTP and BTBP ligands, C5-BPP needs an additional lipophilic anion source such as a 2-bromocarboxylic acid to selectively extract trivalent actinides from nitric acid solutions. The comparison of the stability constant of the (Cm(C5-BPP) 3 ) 3+ complex with the stability constant of the (Cm(nPr-BTP) 3 ) 3+ complex

Actinide recovery techniques utilizing electromechanical processes

International Nuclear Information System (INIS)

Westphal, B.R.; Benedict, R.W.

1994-01-01

Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

Sigma Team for Minor Actinide Separation: PNNL FY 2011 Status Report

Energy Technology Data Exchange (ETDEWEB)

Lumetta, Gregg J.; Braley, Jenifer C.; Sinkov, Sergey I.; Levitskaia, Tatiana G.; Carter, Jennifer C.; Warner, Marvin G.; Pittman, Jonathan W.

2011-08-13

This report summarizes work conducted in FY 2011 at PNNL to investigate new methods of separating the minor actinide elements (Am and Cm) from the trivalent lanthanide elements, and separation of Am from Cm. For the former, work focused on a solvent extraction system combining an acidic extractant (HDEHP) with a neutral extractant (CMPO) to form a hybrid solvent extraction system referred to as TRUSPEAK (combining the TRUEX and TALSPEAK processes). For the latter, ligands that strongly bing uranyl ion were investigated for stabilizing corresponding americyl ion.

Criteria for achieving actinide reduction goals

International Nuclear Information System (INIS)

Liljenzin, J.O.

1996-01-01

In order to discuss various criteria for achieving actinide reduction goals, the goals for actinide reduction must be defined themselves. In this context the term actinides is interpreted to mean plutonium and the so called ''minor actinides'' neptunium, americium and curium, but also protactinium. Some possible goals and the reasons behind these will be presented. On the basis of the suggested goals it is possible to analyze various types of devices for production of nuclear energy from uranium or thorium, such as thermal or fast reactors and accelerator driven system, with their associated fuel cycles with regard to their ability to reach the actinide reduction goals. The relation between necessary single cycle burn-up values, fuel cycle processing losses and losses to waste will be defined and discussed. Finally, an attempt is made to arrange the possible systems on order of performance with regard to their potential to reduce the actinide inventory and the actinide losses to wastes. (author). 3 refs, 3 figs, 2 tabs

Actinide targets for fundamental research in nuclear physics

Science.gov (United States)

Eberhardt, K.; Düllmann, Ch. E.; Haas, R.; Mokry, Ch.; Runke, J.; Thörle-Pospiech, P.; Trautmann, N.

2018-05-01

Thin actinide layers deposited on various substrates are widely used as calibration sources in nuclear spectroscopy. Other applications include fundamental research in nuclear chemistry and -physics, e.g., the chemical and physical properties of super-heavy elements (SHE, Z > 103) or nuclear reaction studies with heavy ions. For the design of future nuclear reactors like fast-fission reactors and accelerator-driven systems for transmutation of nuclear waste, precise data for neutron absorption as well as neutron-induced fission cross section data for 242Pu with neutrons of different energies are of particular importance, requiring suitable Pu-targets. Another application includes studies of nuclear transitions in 229Th harvested as α-decay recoil product from a thin layer of its 233U precursor. For this, a thin and very smooth layer of 233U is used. We report here on the production of actinide layers mostly obtained by Molecular Plating (MP). MP is currently the only fabrication method in cases where the desired actinide material is available only in very limited amounts or possesses a high specific activity. Here, deposition is performed from organic solution applying a current density of 1-2 mA/cm2. Under these conditions target thicknesses of 500-1000 μg/cm2 are possible applying a single deposition step with deposition yields approaching 100 %. For yield determination α-particle spectroscopy, γ-spectroscopy and Neutron Activation Analysis is routinely used. Layer homogeneity is checked with Radiographic Imaging. As an alternative technique to MP the production of thin lanthanide and actinide layers by the so-called "Drop on Demand"-technique applied e.g., in ink-jet printing is currently under investigation.

MOLECULAR SPECTROSCPY AND REACTIONS OF ACTINIDES IN THE GAS PHASE AND CRYOGENIC MATRICES

Energy Technology Data Exchange (ETDEWEB)

Heaven, Michael C.; Gibson, John K.; Marcalo, Joaquim

2009-02-01

temperature or below. For many spectroscopic measurements, low temperatures have been achieved by co-condensing the actinide vapor in rare gas or inert molecule host matrices. Spectra recorded in matrices are usually considered to be minimally perturbed. Trapping the products from gas-phase reactions that occur when trace quantities of reactants are added to the inert host gas has resulted in the discovery of many new actinide species. Selected aspects of the matrix isolation data were discussed in chapter 17. In the present chapter we review the spectroscopic matrix data in terms of its relationship to gas-phase measurements, and update the description of the new reaction products found in matrices to reflect the developments that have occurred during the past two years. Spectra recorded in matrix environments are usually considered to be minimally perturbed, and this expectation is borne out for many closed shell actinide molecules. However, there is growing evidence that significant perturbations can occur for open shell molecules, resulting in geometric distortions and/or electronic state reordering. Studies of actinide reactions in the gas phase provide an opportunity to probe the relationship between electronic structure and reactivity. Much of this work has focused on the reactions of ionic species, as these may be selected and controlled using various forms of mass spectrometry. As an example of the type of insight derived from reaction studies, it has been established that the reaction barriers for An+ ions are determined by the promotion energies required to achieve the 5fn6d7s configuration. Gas-phase reaction studies also provide fundamental thermodynamic properties such as bond dissociation and ionization energies. In recent years, an increased number of gas-phase ion chemistry studies of bare (atomic) and ligated (molecular) actinide ions have appeared, in which relevant contributions to fundamental actinide chemistry have been made. These studies were initiated

Actinides: why are they important biologically

International Nuclear Information System (INIS)

Durbin, P.W.

1978-01-01

The following topics are discussed: actinide elements in energy systems; biological hazards of the actinides; radiation protection standards; and purposes of actinide biological research with regard to toxicity, metabolism, and therapeutic regimens

Interaction study of amino acids and the peptide aspartame with lanthanide (III) ions

International Nuclear Information System (INIS)

Carubelli, C.R.

1990-01-01

The interactions between the Nd(III) ion with the amino acids L-aspartic acid, L-glutamic acid and L-histidine and the peptide aspartame in aqueous solution were studied. The study was conducted by means of electronic spectroscopy with the Judd-Ofelt formalism for transition intensity parameters calculations. Several coordination compounds involving Nd(III), Eu(III), and Tb(III) and the ligands L-histidine and aspartame were synthesized and characterized in the solid state. Mixed compounds involving Eu(III) and Tb(III) with the same ligands were synthesized and characterized also. The characterization were achieved by chemical analysis, melting points, vibrational spectroscopy (IR) and powder X-ray diffractometry. (author)

Electrochemical reduction of actinides oxides in molten salts

International Nuclear Information System (INIS)

Claux, B.

2011-01-01

Reactive metals are currently produced from their oxide by multiple steps reduction techniques. A one step route from the oxide to the metal has been suggested for metallic titanium production by electrolysis in high temperature molten chloride salts. In the so-called FFC process, titanium oxide is electrochemically reduced at the cathode, generating O 2- ions, which are converted on a graphite anode into carbon oxide or dioxide. After this process, the spent salt can in principle be reused for several batches which is particularly attractive for a nuclear application in terms of waste minimization. In this work, the electrochemical reduction process of cerium oxide (IV) is studied in CaCl 2 and CaCl 2 -KCl melts to understand the oxide reduction mechanism. Cerium is used as a chemical analogue of actinides. Electrolysis on 10 grams of cerium oxide are made to find optimal conditions for the conversion of actinides oxides into metals. The scale-up to hundred grams of oxide is also discussed. (author) [fr

Partitioning technologies and actinide science: towards pilot facilities in Europe (ACSEPT project)

International Nuclear Information System (INIS)

Bourg, S.; Hill, C.; Ouvrier, N.

2010-01-01

ACSEPT is an essential contribution to the demonstration, in the long term, of the potential benefits of actinide recycling to minimize the burden on the geological repositories. To succeed, ACSEPT is organized into three technical domains: (i) Considering technically mature aqueous separation processes, ACSEPT works to optimize and select the most promising ones dedicated either to actinide partitioning or to grouped actinide separation. A substantial review was undertaken either to be sure that the right molecule families are being studied, or, on the contrary, to identify new candidates. Results of the first hot tests allowed the validation of some process options. (ii) Concerning pyrochemical separation processes, ACSEPT is focused on the enhancement of the two reference cores of process selected within EUROPART with specific attention to the exhaustive electrolysis in molten chloride (quantitative recovery of the actinides with the lowest amount of fission products) and to actinide back-extraction from an An-Al alloy. R and D efforts are also brought to key scientific and technical issues compulsory for building a complete separation process (head-end steps, salt treatment for recycling and waste management). (iii) By integrating all the experimental results within engineering and systems studies, both in hydro and pyro domains, ACSEPT will deliver relevant flowsheets and recommendations to prepare for future demonstration at a pilot level, in relation with strategies developed through the SNE-TP. In addition, a training and education programme is implemented to share the knowledge among the partitioning community and the future generations of researchers

Lanthanide - actinide separation: a challenge in the back end of nuclear fuel cycle

International Nuclear Information System (INIS)

Mohapatra, P.K.

2015-01-01

Due to their similar size and chemical state, separation of trivalent lanthanide and actinide ions has always been a challenging topic of research. Of late, the growing concern for the radioactive waste management in the back end of the nuclear fuel cycle has led to the possibility of transmuting the long-lived transuranides in high flux reactors. This necessitates the development of processes for the separation of lanthanides and actinides in acidic/low pH media. In view of the high absorption cross section of few lanthanides, their presence in relatively large proportion (10-100 times) impedes the transmutation process. Processes such as the TRAMEX and TALSPEAK have been used for the separation of lanthanides from trivalent actinides. Of late soft donor ligands containing S and N donor atoms have been used for the selective extraction of trivalent actinide ions. The commercially available S-donor compound, CYANEX 301 (bis(2,4,4-trimethylpentyl) dithiophosphinic acid) has been used to yield separation factor (S.F.) values in the excess of 6000. Synergistic extraction with N-donor ligands such as 2,2'-bipyridyl and 1,10-phenanthroline have yielded S.F. values close to 40,000. N-donor ligands such as BTP (bis-triazinylpyridine), BTBP (bis-triazinylbipyridyl) and BTPhen (bis-triazinyl-phenanthroline) have been particularly effective from relatively acidic feed conditions. The present lecture will give a brief outline of the separation processes and experimental results of studies carried out using various S and N donor ligands. Use of room temperature ionic liquids for more favorable separations will be highlighted. Liquid membrane separation results for application to back end nuclear fuel cycle will also be discussed. (author)

Actinide recovery techniques utilizing electromechanical processes

International Nuclear Information System (INIS)

Westphal, B.R.; Benedict, R.W.

1994-01-01

Under certain conditions, the separation of actinides using electromechanical techniques may be an effective means of residue processing. The separation of granular mixtures of actinides and other materials discussed in this report is based on appreciable differences in the magnetic and electrical properties of the actinide elements. In addition, the high density of actinides, particularly uranium and plutonium, may render a simultaneous separation based on mutually complementary parameters. Both high intensity magnetic separation and electrostatic separation have been investigated for the concentration of an actinide waste stream. Waste stream constituents include an actinide metal alloy and broken quartz shards. The investigation of these techniques is in support of the Integral Fast Reactor (IFR) concept currently being developed at Argonne National Laboratory under the auspices of the Department of Energy

Effect of pH on stability constants of Am(III)- and Cm(III)- humate complexes

International Nuclear Information System (INIS)

Samadfam, Mohammad; Jintoku, Takashi; Sato, Seichi; Ohashi, Hiroshi; Mitsugashira, Toshiaki; Hara, Mitsuo; Suzuki, Yoshimitsu

1999-01-01

The apparent stability constants of Am(III)- and Cm(III)-humate complexes were determined by dialysis method at ionic strength 0.1 in the pH range from 3.3 to 5.7 under N 2 bubbling. The Am(III) and Cm(III) loadings were about 10 -7 and 10 -10 mol/dm 3 . The concentrations of Am-241 and Cm-242 tracers were measured by α-spectrometry. It was found that the apparent stability constants were almost identical for both the Am(III)-humate and Cm(III)-humate complexes. The apparent stability constants showed a small pH-dependence, increasing from 10 4.6 at pH 3.3 to 10 5.1 at pH 5.7. The ionization of acidic functional groups of humic acid is possibly the primary factor. Above pH 6, the dialysis membrane was no langer permeable to Am(III) and Cm(III) ions and the apparent stability constant could not be experimentally obtained. The apparent stability constants between pH 6 and pH 8.5 were evaluated by considering that both binary metal-humate and ternary metal-hydroxo-humate complexes exist at pHs above 6. It was assumed that mono-hydroxo-humate complex Am(OH)HA and Cm(OH)HA are the major ternary complexes that exist below pH 9. The overall stability constants for Am(III)- and Cm(III)-humate complexes increased from 10 5.7 at pH 6 to 10 7.2 at pH 8. This implies that the formation of metal-hydroxo-humate species is preferred over the formation of hydroxide species. The apparent overall stability constants can be easily incorporated into geochemical modeling of trivalent actinide migration. The results of the present study show that the apparent stability constants determined experimentally at pH≤6 do not represent the complexation properties at higher pHs and the formation of ternary complexes should be considered in speciation calculations of radionuclides at terrestrial environment. (J.P.N.)

Potentiometric Sensor for Gadolinium(III Ion Based on Zirconium(IV Tungstophosphate as an Electroactive Material

Directory of Open Access Journals (Sweden)

Harish K. Sharma

2009-01-01

Full Text Available A new inorganic ion exchanger has been synthesized namely Zirconium(IV tungstophosphate [ZrWP]. The synthesized exchanger was characterized using ion exchange capacity and distribution coefficient (Kd. For further studies, exchanger with 0.35 meq/g ion-exchange capacity was selected. Electrochemical studies were carried out on the ion exchange membranes using epoxy resin as a binder. In case of ZrWP, the membrane having the composition; Zirconium(IV tugstophosphate (40% and epoxy resin (60% exhibits best performance. The membrane works well over a wide range of concentration from 1×10-5 to 1×10-1 M of Gd(III ion with an over- Nernstian slope of 30 mv/ decade. The response time of the sensor is 15 seconds. For this membrane, effect of internal solution has been studied and the electrode was successfully used in partially non-aqueous media too. Fixed interference method and matched potential method has been used for determining selectivity coefficient with respect to alkali, alkaline earth, some transition and rare earth metal ions that are normally present along with Gd(III in its ores. The electrode can be used in the pH range 4.0-10.0 for 10-1 M and 3.0-7.0 for 10-2 M concentration of target ion. These sensors have been used as indicator electrodes in the potentiometric titration of Gd(III ion against EDTA and oxalic acid.

Research on the chemical speciation of actinides

International Nuclear Information System (INIS)

Jung, Euo Chang; Park, K. K.; Cho, H. R.

2010-04-01

A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using advanced laser-based highly sensitive spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been performed for the chemical speciation of actinide in an aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. (1) Development of TRLFS technology for chemical speciation of actinides, (2) Development of LIBD technology for measuring solubility of actinides, (3) Chemical speciation of plutonium complexes by using a LWCC system, (4) Development of LIBS technology for the quantitative analysis of actinides, (5) Development of technology for the chemical speciation of actinides by CE, (6) Evaluation on the chemical reactions between actinides and humic substances, (7) Chemical speciation of actinides adsorbed on metal oxides surfaces, (8) Determination of actinide source terms of spent nuclear fuel

Actinide Separation Demonstration Facility, Tarapur

International Nuclear Information System (INIS)

Vishwaraj, I.

2017-01-01

Partitioning of minor actinide from high level waste could have a substantial impact in lowering the radio toxicity associated with high level waste as well as it will reduce the burden on geological repository. In Indian context, the partitioned minor actinide could be routed into the fast breeder reactor systems scheduled for commissioning in the near period. The technological breakthrough in solvent development has catalyzed the partitioning programme in India, leading to the setting up and hot commissioning of the Actinide Separation Demonstration Facility (ASDF) at BARC, Tarapur. The engineering scale Actinide Separation Demonstration Facility (ASDF) has been retrofitted in an available radiological hot cell situated adjacent to the Advanced Vitrification Facility (AVS). This location advantage ensures an uninterrupted supply of high-level waste and facilitates the vitrification of the high-level waste after separation of minor actinides

Interaction of Eu(III) and Cm(III) with mucin. A key component of the human mucosa

International Nuclear Information System (INIS)

Wilke, Claudia; Barkleit, Astrid

2017-01-01

To evaluate the potential health risks caused by the ingestion of lanthanides (Ln) and actinides (An), investigations into the chemical behavior of these metals in the human gastrointestinal tract are necessary. Mucin is an important part of the protective mucosa layer in the digestive system. We have recently reported that mucin interacts strongly with Eu(III) and Cm(III), representatives of Ln(III) and An(III), respectively, under in vivo conditions. In order to investigate the complexation behavior of this protein with Ln(III)/An(III), TRLFS measurements were performed on Eu(III)/Cm(III)-mucin solutions with different protein concentrations and at different pH. The results indicate the formation of at least two independent mucin species. At higher pH, the formation of hydroxide species was also observed.

Interaction of Eu(III) and Cm(III) with mucin. A key component of the human mucosa

Energy Technology Data Exchange (ETDEWEB)

Wilke, Claudia; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Chemistry of the F-Elements

2017-06-01

To evaluate the potential health risks caused by the ingestion of lanthanides (Ln) and actinides (An), investigations into the chemical behavior of these metals in the human gastrointestinal tract are necessary. Mucin is an important part of the protective mucosa layer in the digestive system. We have recently reported that mucin interacts strongly with Eu(III) and Cm(III), representatives of Ln(III) and An(III), respectively, under in vivo conditions. In order to investigate the complexation behavior of this protein with Ln(III)/An(III), TRLFS measurements were performed on Eu(III)/Cm(III)-mucin solutions with different protein concentrations and at different pH. The results indicate the formation of at least two independent mucin species. At higher pH, the formation of hydroxide species was also observed.

Separation of Am(III) from Eu(III) by mixtures of triazynylbipyridine and bis(dicarbollide) extractants. The composition of the metal complexes extracted

International Nuclear Information System (INIS)

Narbutt, J.; Krejzler, J.

2006-01-01

Separation of trivalent actinides, in particular americium and curium, from lanthanides is an important step in an advanced partitioning process for future reprocessing of spent nuclear fuels. The use of soft donor (N and S) ligands makes it possible to separate the two groups of elements, probably because of the more covalent character in the complexes with actinides compared to the lanthanides. The aim of present work was to study solvent extraction of Am(III) and Eu(III) in a similar system with diethylhemi-BTP and COSAN: protonated bis(chlorodicarbollido)cobalt(III) or commo-3,3-cobalta-bis(8,9,12-trichlora-1,2-dicarbaclosododecaborane)ic acid. The present research was focused on both the determination of conditions for the separation of 241 Am(III) from 152 Eu in aqueous nitrate solution by using a synergistic extraction system and on the modelling of the process by slope analysis. Obtained values of the separation factors supported by the computer modelling permitted drawing the conclusions on the mechanism of the process and on the structure of extracted species

Partitioning of Minor Actinides from High Active Raffinates using Bis-Diglycol-amides (BisDGA) as new efficient Extractants

Energy Technology Data Exchange (ETDEWEB)

Modolo, G.; Vijgen, H. [Forschungszentrum Juelich GmbH, Institute for Energy Research, Safety Research and Reactor Technology, 52425 Juelich (Germany); Espartero, A.G. [Centro de Investigaciones Energeticas, Medioambientales y Tecnologicas (CIEMAT), Avda. Complutense 22, 28040-Madrid (Spain); Prados, P. [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Mendoza, J. de [Departamento de Quimica Organica, Facultad de Ciencias, Universidad Autonoma de Madrid - UAM, carretera de Colmenar Viejo km 15.3, 28049-Madrid (Spain); Institut Catala d' Investigacio Quimica (ICIQ) Av. Paisos Catalans 16, 43007-Tarragona (Spain)

2008-07-01

Two new polyamide extractants has been selected, namely UAM-069 and UAM-081, both synthesized at the University of Madrid (UAM), to develop a new separation process. These two ligands are bis-diglycol-amides, consisting of two diglycol-amides moieties grafted on an aromatic platform (UAM-069) or on an aliphatic linker (UAM-081), respectively. The extraction of actinides and fission products was studied from synthetic PUREX raffinate. Actinides(III) and lanthanides(III) are highly extracted from acidities > 1 mol/L HNO{sub 3}. The extraction of Zr, Mo and Pd could be suppressed with complexing agents such as oxalic acid and HEDTA. In the present paper the results of the batch extraction results are presented which serve for the development of a new continuous counter current process to be tested in centrifugal contactors. (authors)

Subsurface Biogeochemistry of Actinides

Energy Technology Data Exchange (ETDEWEB)

Kersting, Annie B. [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Univ. Relations and Science Education; Zavarin, Mavrik [Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Glenn T. Seaborg Inst.

2016-06-29

A major scientific challenge in environmental sciences is to identify the dominant processes controlling actinide transport in the environment. It is estimated that currently, over 2200 metric tons of plutonium (Pu) have been deposited in the subsurface worldwide, a number that increases yearly with additional spent nuclear fuel (Ewing et al., 2010). Plutonium has been shown to migrate on the scale of kilometers, giving way to a critical concern that the fundamental biogeochemical processes that control its behavior in the subsurface are not well understood (Kersting et al., 1999; Novikov et al., 2006; Santschi et al., 2002). Neptunium (Np) is less prevalent in the environment; however, it is predicted to be a significant long-term dose contributor in high-level nuclear waste. Our focus on Np chemistry in this Science Plan is intended to help formulate a better understanding of Pu redox transformations in the environment and clarify the differences between the two long-lived actinides. The research approach of our Science Plan combines (1) Fundamental Mechanistic Studies that identify and quantify biogeochemical processes that control actinide behavior in solution and on solids, (2) Field Integration Studies that investigate the transport characteristics of Pu and test our conceptual understanding of actinide transport, and (3) Actinide Research Capabilities that allow us to achieve the objectives of this Scientific Focus Area (SFA and provide new opportunities for advancing actinide environmental chemistry. These three Research Thrusts form the basis of our SFA Science Program (Figure 1).

Concentration of actinides in the food chain

International Nuclear Information System (INIS)

Bulman, R.A.

1976-06-01

Considerable concern is now being expressed over the discharge of actinides into the environment. This report presents a brief review of the chemistry of the actinides and examines the evidence for interaction of the actinides with some naturally-occurring chelating agents and other factors which might stimulate actinide concentration in the food chain of man. This report also reviews the evidence for concentration of actinides in plants and for uptake through the gastrointestinal tract. (author)

Thermal-hydraulics of actinide burner reactors

International Nuclear Information System (INIS)

Takizuka, Takakazu; Mukaiyama, Takehiko; Takano, Hideki; Ogawa, Toru; Osakabe, Masahiro.

1989-07-01

As a part of conceptual study of actinide burner reactors, core thermal-hydraulic analyses were conducted for two types of reactor concepts, namely (1) sodium-cooled actinide alloy fuel reactor, and (2) helium-cooled particle-bed reactor, to examine the feasibility of high power-density cores for efficient transmutation of actinides within the maximum allowable temperature limits of fuel and cladding. In addition, calculations were made on cooling of actinide fuel assembly. (author)

PVC-membrane potentiometric sensors based on a recently synthesized Schiff base for Fe(III ion

Directory of Open Access Journals (Sweden)

S. Yousef Ebrahimipur

2012-12-01

Full Text Available A potentiometric iron sensor based on the use 3-(2-diethylamino-ethylimino-1,3-dihydro-indol-2-one (DEDIO as an ionophore in poly(vinyl chloride (PVC matrix, is reported. The plasticized membrane sensor exhibits a Nernstian response for Fe(III ions over a wide concentration range (2.0 × 10-6 - 5.0 × 10-2 M with a super Nernstian slope of 26(plus or minus 1 mV per decade. It has a fast response time of less than 12 s and can be used for ten weeks without any considerable divergences in its potentials the electrode can be used in the pH range 4.5-8.0. The proposed sensor shows fairly good discriminating ability towards Fe(III ion in comparison with a large number of alkali, alkaline earth, transition and heavy metal ions. The sensor was used as indicator electrode in potentiometric titration of Fe(III ions vs. EDTA.DOI: http://dx.doi.org/10.4314/bcse.v26i1.7

Remarkably High Stability of Late Actinide Dioxide Cations: Extending Chemistry to Pentavalent Berkelium and Californium.

Science.gov (United States)

Dau, Phuong D; Vasiliu, Monica; Peterson, Kirk A; Dixon, David A; Gibson, John K

2017-12-06

Actinyl chemistry is extended beyond Cm to BkO 2 + and CfO 2 + through transfer of an O atom from NO 2 to BkO + or CfO + , establishing a surprisingly high lower limit of 73 kcal mol -1 for the dissociation energies, D[O-(BkO + )] and D[O-(CfO + )]. CCSD(T) computations are in accord with the observed reactions, and characterize the newly observed dioxide ions as linear pentavalent actinyls; these being the first Bk and Cf species with oxidation states above IV. Computations of actinide dioxide cations AnO 2 + for An=Pa to Lr reveal an unexpected minimum for D[O-(CmO + )]. For CmO 2 + , and AnO 2 + beyond EsO 2 + , the most stable structure has side-on bonded η 2 -(O 2 ), as An III peroxides for An=Cm and Lr, and as An II superoxides for An=Fm, Md, and No. It is predicted that the most stable structure of EsO 2 + is linear [O=Es V =O] + , einsteinyl, and that FmO 2 + and MdO 2 + , like CmO 2 + , also have actinyl(V) structures as local energy minima. The results expand actinide oxidation state chemistry, the realm of the distinctive actinyl moiety, and the non-periodic character towards the end of the periodic table. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ion-Selective Electrode for the Determination of Iron(III in Vitamin Formulations

Directory of Open Access Journals (Sweden)

Teixeira Marcos Fernando de S.

1998-01-01

Full Text Available A coated graphite-epoxy ion-selective electrode for iron(III, based on the ion-pair formed between [Fe(citrate2]3- and the tricaprylylmethylammonium cation (Aliquat 336 in a poly(vinylchloride (PVC matrix has been constructed. A thin membrane film of this ion-pair, dibutylphthalate (DBPh in PVC was deposited directly onto a Perspex® tube, which contained a graphite-epoxy conductor substrate. The coating solution was prepared by dissolving 30% (w/w of PVC in 10 mL of tetrahydrofuran following addition of 65% (w/w DBPh and 5% (w/w of the ionic pair. The effect of pH, citrate concentration and some cations on the electrode response has been investigated. The E(mV vs. log [Fe(citrate2]3- electrode response was linear for iron(III concentration from 1.0 x 10-3 mol/L to 1.0 x 10-1 mol/L in 1.0 mol/L citrate medium, with a slope of 19.3 ± 0.5 mV/decade and a useful lifetime of at least six months (more than 800 determinations for each polymeric membrane used. The detection limit was 7.5 x 10-4 mol/L and the relative standard deviation was less than 3% for a solution containing 5.0 x 10-3 mol/L of iron(III (n = 10. The application of this electrode for iron(III determination in samples of vitamin formulations is described. The results obtained with this procedure are in close agreement with those obtained using AA spectrophotometry (r = 0.9999.

Advanced Aqueous Separation Systems for Actinide Partitioning

Energy Technology Data Exchange (ETDEWEB)

Nash, Ken [Washington State Univ., Pullman, WA (United States); Martin, Leigh [Idaho National Lab. (INL), Idaho Falls, ID (United States); Lumetta, Gregg [Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

2015-04-02

One of the most challenging aspects of advanced processing of used nuclear fuel is the separation of transplutonium actinides from fission product lanthanides. This separation is essential if actinide transmutation options are to be pursued in advanced fuel cycles, as lanthanides compete with actinides for neutrons in both thermal and fast reactors, thus limiting efficiency. The separation is difficult because the chemistry of Am3+ and Cm3+ is nearly identical to that of the trivalent lanthanides (Ln3+). The prior literature teaches that two approaches offer the greatest probability of devising a successful group separation process based on aqueous processes: 1) the application of complexing agents containing ligand donor atoms that are softer than oxygen (N, S, Cl-) or 2) changing the oxidation state of Am to the IV, V, or VI state to increase the essential differences between Am and lanthanide chemistry (an approach utilized in the PUREX process to selectively remove Pu4+ and UO22+ from fission products). The latter approach offers the additional benefit of enabling a separation of Am from Cm, as Cm(III) is resistant to oxidation and so can easily be made to follow the lanthanides. The fundamental limitations of these approaches are that 1) the soft(er) donor atoms that interact more strongly with actinide cations than lanthanides form substantially weaker bonds than oxygen atoms, thus necessitating modification of extraction conditions for adequate phase transfer efficiency, 2) soft donor reagents have been seen to suffer slow phase transfer kinetics and hydro-/radiolytic stability limitations and 3) the upper oxidation states of Am are all moderately strong oxidants, hence of only transient stability in media representative of conventional aqueous separations systems. There are examples in the literature of both approaches having been described. However, it is not clear at present that any extant process is sufficiently robust for application at the scale

Retention behavior of actinides and long lived fission products on Smectite rich clays

International Nuclear Information System (INIS)

Tomar, B.S.

2014-01-01

In the present work, sorption of Am(llI), Cs(I) and Sr(ll) by the Smectite rich clay from western India has been studied in detail under the varying experimental conditions, viz., pH, ionic strength, and metal ion concentration. The experimental data on sorption have been modeled using the surface complexation model. Am(llI) sorption by smectite rich clay was found to increase with the pH of the suspension. At lower pH values, the sorption decreased with increasing ionic strength of the suspension, but remained constant at higher pH values. This is reminiscent of the ion exchange mechanism at lower pH and predominantly inner sphere complexation at higher pH. Surface complexation modeling using FITEQL could successfully explain these two mechanisms operating in the different pH values. Sorption of Cs(I) and Sr(II) by the smectite rich clay was studied under the varying experimental conditions. Though the sorption of both the metal ions increased with pH, it decreased with the increasing ionic strength, at all pH values, suggesting ion exchange as the predominant mechanism at all pH values. Further, the ionic strength dependence was different in the case of Cs(I) and Sr(II) depending upon the metal ion concentration. At same metal ion concentration of Cs(I) and Sr(II) (10 -5 M) the extent of decrease with ionic strength was same in both cases, while at 10 -9 M, Cs(I), the decrease was much smaller than that at 10 -5 M. This indicates the existence of ion exchange sites having different affinities. These studies have shown high retention capacity of the clay for actinides and long lived fission products with the sorption following ion exchange mechanism in the case of Cs(I) and Sr(II) and a combination of ion exchange and surface complexation in the case of Am(III) depending upon the pH. The sorption data could be successfully explained within the framework of FITEQL, taking into account both the types of binding sites

ACSEPT-Partitioning technologies and actinide science: Towards pilot facilities in Europe

International Nuclear Information System (INIS)

Bourg, S.; Hill, C.; Caravaca, C.; Rhodes, C.; Ekberg, C.; Taylor, R.; Geist, A.; Modolo, G.; Cassayre, L.; Malmbeck, R.; Harrison, M.; Angelis, G. de; Espartero, A.; Bouvet, S.; Ouvrier, N.

2011-01-01

Highlights: → ACSEPT works at developing actinide separation processes for advanced fuel cycles. → ACSEPT develops both aqueous and pyrochemical actinide separation processes. → Homogeneous and heterogeneous recycling strategies are both considered in ACSEPT. → Training and education in actinide chemistry are important issues addressed by ACSEPT. - Abstract: Actinide recycling by separation and transmutation is considered worldwide and particularly in several European countries as one of the most promising strategies to reduce the inventory of radioactive waste and to optimise the use of natural resources. With its multidisciplinary consortium of 34 partners from 12 European countries plus Australia and Japan, the European Research Project ACSEPT (Actinide reCycling by SEParation and Transmutation) aims at contributing to the development of this strategy by studying both hydrometallurgical and pyrochemical partitioning routes. ACSEPT is organised into three technical domains: (i)Considering technically mature aqueous separation processes, ACSEPT works to optimise and select the most promising ones dedicated either to actinide partitioning (for the heterogeneous recycling of actinides in ADS target or specific actinide bearing blanket fuels in fast reactor) or to grouped actinide separation (for the homogeneous recycling of the actinides in fast reactor fuels). In addition, dissolution and conversion studies are underway taking into account the specific requirements of these specific fuels. (ii)Concerning pyrochemical separation processes, ACSEPT focuses on the enhancement of the two reference cores processes selected within FP6-EUROPART. R and D efforts are also devoted to key scientific and technical issues compulsory to set up a complete separation process (head-end steps, salt treatment for recycling and waste management). (iii)By integrating all the experimental results in engineering and system studies, both in hydro and pyro domains, ACSEPT will

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

International Nuclear Information System (INIS)

Eliseeva, Svetlana V.; Golovach, Iurii P.; Liasotskyi, Valerii S.; Antonovich, Valery P.; Petoud, Stéphane; Meshkova, Svetlana B.

2016-01-01

Most of the existing optical methods for Cu II detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a "turn-on" lanthanide(III)-based molecular probe for the specific detection of Cu II ions based on both visible (Tb III , Eu III ) and near-infrared (Nd III , Yb III ) emission. Quantum yields of the characteristic Ln III emission signals increases by at least two-orders of magnitude upon addition of Cu II into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu II ions does not significantly affect the energy positions of the singlet (32,260 cm −1 ) and triplet (25,640–25,970 cm −1 ) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu II to Cu I has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu II over other transition metal ions: the addition of divalent Zn II , Cd II , Pd II , Ni II , Co II or trivalent Fe III , Ga III , In III ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu II results in a 20- to 30-times lanthanide luminescence enhancement. This new strategy results in a versatile and selective optical platform for the

Highly Sensitive Aluminium(III) Ion Sensor Based on a Self-assembled Monolayer on a Gold Nanoparticles Modified Screen-printed Carbon Electrode.

Science.gov (United States)

See, Wong Pooi; Heng, Lee Yook; Nathan, Sheila

2015-01-01

A new approach for the development of a highly sensitive aluminium(III) ion sensor via the preconcentration of aluminium(III) ion with a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode and current mediation by potassium ferricyanide redox behavior during aluminium(III) ion binding has been attempted. A monolayer of mercaptosuccinic acid served as an effective complexation ligand for the preconcentration of trace aluminium; this led to an enhancement of aluminium(III) ion capture and thus improved the sensitivity of the sensor with a detection limit of down to the ppb level. Under the optimum experimental conditions, the sensor exhibited a wide linear dynamic range from 0.041 to 12.4 μM. The lower detection limit of the developed sensor was 0.037 μM (8.90 ppb) using a 10 min preconcentration time. The sensor showed excellent selectivity towards aluminium(III) ion over other interference ions.

Actinide colloid generation in groundwater. Part 2

International Nuclear Information System (INIS)

Kim, J.I.

1991-01-01

The progress made in the investigation of actinide colloid generation in groundwater is summarized and discussed with particular examples relevant to an understanding of the migration behaviour of actinides in natural aquifer systems. The first part deals with the characterization of colloids: groundwater colloids, actinide real-colloids and actinide pseudocolloids. The second part concentrates on the generation processes and migration behaviour of actinide pseudo colloids, which are discussed with some notable experimental examples. Importance is stressed more on the chemical aspects of the actinide colloid generation in groundwater. This work is a contribution to the CEC Mirage II project, in particular the complexation and colloids research area

Actinide cation-cation complexes

International Nuclear Information System (INIS)

Stoyer, N.J.; Seaborg, G.T.

1994-12-01

The +5 oxidation state of U, Np, Pu, and Am is a linear dioxo cation (AnO 2 + ) with a formal charge of +1. These cations form complexes with a variety of other cations, including actinide cations. Other oxidation states of actinides do not form these cation-cation complexes with any cation other than AnO 2 + ; therefore, cation-cation complexes indicate something unique about AnO 2 + cations compared to actinide cations in general. The first cation-cation complex, NpO 2 + ·UO 2 2+ , was reported by Sullivan, Hindman, and Zielen in 1961. Of the four actinides that form AnO 2 + species, the cation-cation complexes of NpO 2 + have been studied most extensively while the other actinides have not. The only PuO 2 + cation-cation complexes that have been studied are with Fe 3+ and Cr 3+ and neither one has had its equilibrium constant measured. Actinides have small molar absorptivities and cation-cation complexes have small equilibrium constants; therefore, to overcome these obstacles a sensitive technique is required. Spectroscopic techniques are used most often to study cation-cation complexes. Laser-Induced Photacoustic Spectroscopy equilibrium constants for the complexes NpO 2 + ·UO 2 2+ , NpO 2 + ·Th 4+ , PuO 2 + ·UO 2 2+ , and PuO 2 + ·Th 4+ at an ionic strength of 6 M using LIPAS are 2.4 ± 0.2, 1.8 ± 0.9, 2.2 ± 1.5, and ∼0.8 M -1

Complexation of metal ions with humic acid: charge neutralization model

International Nuclear Information System (INIS)

Kim, J.I.; Czerwinski, K.R.

1995-01-01

A number of different approaches are being used for describing the complexation equilibrium of actinide ions with humic or fulvic acid. The approach chosen and verified experimentally by Tu Muenchen will be discussed with notable examples from experiment. This approach is based on the conception that a given actinide ion is neutralized upon complexation with functional groups of humic or fulvic acid, e.g. carboxylic and phenolic groups, which are known as heterogeneously cross-linked polyelectrolytes. The photon energy transfer experiment with laser light excitation has shown that the actinide ion binding with the functional groups is certainly a chelation process accompanied by metal ion charge neutralization. This fact is in accordance with the experimental evidence of the postulated thermodynamic equilibrium reaction. The experimental results are found to be independent of origin of humic or fulvic acid and applicable for a broad range of pH. (authors). 23 refs., 7 figs., 1 tab

Ion Implantation in III-V Compound Semiconductors

Science.gov (United States)

1984-09-01

340 keV H + -0 Ga P  O UES-723-292 !:• (H o>ray *P-K X - rayO Ga-K X -ray iii! RBS * ..I -iO.. 0 10I to1. 01 • .0 -. I0 1 LI =i, O I 0 01 0.J 10...Identity by blo ," pume) Ion Implantation, GaAs, Hall effect, electrical resistivity, Rutherford Backscattering (RBS), channeling, Proton induced x -ray...Mebility (jH) upon Aiinealing Temperature (TA) for 1 X 101 /cm• Dose Samples of GaAs:Mg with Three Different Capping Methods 33 p 14 Dependence of Surface

Extraction chromatogrpahy of actinides, ch. 7

International Nuclear Information System (INIS)

Mueller, W.

1975-01-01

This review on extraction chromatography of actinides emphasizes the important usage of neutral (Tributylphosphate), basic (substituted ammonium salts), and acidic (HDEHP) extractants, and their application to separations of actinides in the di-to hexavalent oxidation state. Furthermore, the actinide extraction by ketones, ethers, alcohols and β-diketones is discussed

Comparison of the thermodynamic properties and high temperature chemical behavior of lanthanide and actinide oxides

International Nuclear Information System (INIS)

Ackermann, R.J.; Rauh, E.G.

1977-01-01

The thermodynamic properties of the lanthanide and actinide oxides are examined, compared, and associated with a variety of high temperature chemical behavior. Trends are cited resulting from a number of thermodynamic and spectroscopic correlations involving solid phases, species in aqueous solution, and molecules and ions in the vapor phase. Inadequacies in the data and alternative approaches are discussed. The characterization of nonstoichiometric phases stable only at high temperatures is related to a network of heterogeneous and homogeneous equilibria. A broad perspective of similarity and dissimilarity between the lanthanides and actinides emerges and forms the basis of the projected needs for further study

Mixed Metal Phosphonate- Phosphate Resins for Separation of Lanthanides from Actinides

International Nuclear Information System (INIS)

Clearfield, Abraham

2017-01-01

As indicated in the previous annual report the goals of this project are to develop procedures for efficient separation of lanthanides from actinides and curium from americium. These processes are required for the nuclear fuel cycle to minimize the waste and recover the valuable actinides. The basis for our study is that we have prepared a group of compounds that are porous and favor the uptake of ions with charges 3+ and 4+ over ions of lesser charge. The general formula for these materials is M(O 3 PC 6 H 4 PO 3 ) 1-x/2 (APO 4 )x·nH 2 O: where M=Zr 4+ , Sn 4+ , A=H, Na, or K and X=O, 0.5, 0.8, 1.0, 1.33 and 1.61-3. One of our tasks is to determine which members of this group of compounds are effective in carrying out the required separations. A difficulty in obtaining this required information is that the compounds are amorphous. That is they are not crystalline, therefore we need to resort to synchrotron data to obtain structural data which will be presented in detail. This information will be provided as a separate section.

Evaluation and testing of sequestering agents for the removal of actinides from waste streams

Energy Technology Data Exchange (ETDEWEB)

Hoffman, D.C.; Romanovski, V.V.; Veeck, A.C. [Lawrence Livermore National Lab., CA (United States)] [and others

1997-10-01

The purpose of this project is to evaluate and test the complexing ability of a variety of promising new complexing agents synthesized by Professor Kenneth Raymond`s group at the University of California, Berkeley (ESP-CP TTP Number SF16C311). Some of these derivatives have already shown the potential for selectivity binding Pu(IV) in a wide range of solutions in the presence of other metals. Professor Raymond`s group uses molecular modeling to design and synthesize ligands based on modification of natural siderophores, or their analogs, for chelation of actinides. The ligands are then modified for use as liquid/liquid and solid/liquid extractants. The authors` group at the Glenn T. Seaborg Institute for Transactinium Science (ITS) at Lawrence Livermore National Laboratory determines the complex formation constants between the ligands and actinide ions, the capacity and time dependence for uptake on the resins, and the effect of other metal ions and pH.

Position of actinide elements in the periodic table : evolution of a generalised form (Preprint no. SSC-33)

International Nuclear Information System (INIS)

Nathaniel, T.N.

1991-01-01

All the actinides and lanthanides are placed in III group and are shown separately, in the most popular forms of the periodic table, including the latest version of IUPAC. This has been leading to an avoidable debate i.e. whether to place La and Ac or Lu and Lw below Sc and Y in the III-B group. Apart from this, the group characteristic nature of most of the actinides elements, demands that a more appropriate position is to be given to these f block elements. The situation is more complex in the higher periods, in which new elements belonging to g block, h block, ... are to be included. Also, there seems to be no consensus in following a uniform and acceptable subgroup notation. The author arrived at a new form of the periodic table to successfully sort out all these issues. The table is presented. (author). 10 refs., 1 fig

The Cathodic Behavior of Ti(III) Ion in a NaCl-2CsCl Melt

Science.gov (United States)

Song, Yang; Jiao, Shuqiang; Hu, Liwen; Guo, Zhancheng

2016-02-01

The cathodic behavior of Ti(III) ions in a NaCl-2CsCl melt was investigated by cyclic voltammetry, chronopotentiometry, and square wave voltammetry with a tungsten electrode being the working electrode at different temperatures. The results show that the cathodic behavior of Ti(III) ion consists of two irreversible steps: Ti3+ + e = Ti2+ and Ti2+ + 2 e = Ti. The diffusion coefficient for the Ti(III) ion in the NaCl-2CsCl eutectic is 1.26 × 10-5 cm2 s-1 at 873 K (600 °C), increases to be 5.57 × 10-5 cm2 s-1 at 948K (675°C), and further rises to 10.8 × 10-5 cm2 s-1 at 1023 (750 °C). Moreover, galvanostatic electrolysis performed on a titanium electrode further presents the feasibility of electrodepositing metallic titanium in the molten NaCl-2CsCl-TiCl3 system.

An ultrahigh vacuum, low-energy ion-assisted deposition system for III-V semiconductor film growth

Science.gov (United States)

Rohde, S.; Barnett, S. A.; Choi, C.-H.

1989-06-01

A novel ion-assisted deposition system is described in which the substrate and growing film can be bombarded with high current densities (greater than 1 mA/sq cm) of very low energy (10-200 eV) ions. The system design philosophy is similar to that used in III-V semiconductor molecular-beam epitaxy systems: the chamber is an all-metal ultrahigh vacuum system with liquid-nitrogen-cooled shrouds, Knudsen-cell evaporation sources, a sample insertion load-lock, and a 30-kV reflection high-energy electron diffraction system. III-V semiconductor film growth is achieved using evaporated group-V fluxes and group-III elemental fluxes sputtered from high-purity targets using ions extracted from a triode glow discharge. Using an In target and an As effusion cell, InAs deposition rates R of 2 microns/h have been obtained. Epitaxial growth of InAs was observed on both GaSb(100) and Si(100) substrates.

Minor actinide transmutation on PWR burnable poison rods

International Nuclear Information System (INIS)

Hu, Wenchao; Liu, Bin; Ouyang, Xiaoping; Tu, Jing; Liu, Fang; Huang, Liming; Fu, Juan; Meng, Haiyan

2015-01-01

Highlights: • Key issues associated with MA transmutation are the appropriate loading pattern. • Commercial PWRs are the only choice to transmute MAs in large scale currently. • Considerable amount of MA can be loaded to PWR without disturbing k eff markedly. • Loading MA to PWR burnable poison rods for transmutation is an optimal loading pattern. - Abstract: Minor actinides are the primary contributors to long term radiotoxicity in spent fuel. The majority of commercial reactors in operation in the world are PWRs, so to study the minor actinide transmutation characteristics in the PWRs and ultimately realize the successful minor actinide transmutation in PWRs are crucial problem in the area of the nuclear waste disposal. The key issues associated with the minor actinide transmutation are the appropriate loading patterns when introducing minor actinides to the PWR core. We study two different minor actinide transmutation materials loading patterns on the PWR burnable poison rods, one is to coat a thin layer of minor actinide in the water gap between the zircaloy cladding and the stainless steel which is filled with water, another one is that minor actinides substitute for burnable poison directly within burnable poison rods. Simulation calculation indicates that the two loading patterns can load approximately equivalent to 5–6 PWR annual minor actinide yields without disturbing the PWR k eff markedly. The PWR k eff can return criticality again by slightly reducing the boric acid concentration in the coolant of PWR or removing some burnable poison rods without coating the minor actinide transmutation materials from PWR core. In other words, loading minor actinide transmutation material to PWR does not consume extra neutron, minor actinide just consumes the neutrons which absorbed by the removed control poisons. Both minor actinide loading patterns are technically feasible; most importantly do not need to modify the configuration of the PWR core and

Diamond for Actinide Traces Detection and Spectrometry in Liquids

International Nuclear Information System (INIS)

Pomorski, Michal; Mer, Christine; Sanoit, Jacques-de; Tran, Thuan-Quang; Bergonzo, Philippe

2013-06-01

We describe here a new approach for the detection and identification of actinides (Am, Pu, Cm etc) at very low activity levels in aqueous solution. The measurement consists at first in the electro-precipitation of the actinides ions as insoluble hydroxides directly onto a boron doped nanocrystalline diamond (BNCD) electrode deposited on an α-particle detector (Si or Si-PIN diode), followed by α-particles detection using front-end nuclear electronics. After α-particles counting, spectrometry, the detector can be easily decontaminated using anodization in aqueous solution to be able to be reused at once. The detection limit of the described prototype system can be estimated as low as a few mBq=L (for one day counting) to several mBq=L for 5 h counting and currently achieved energy resolution amounts to ΔE FW HM /E α = 2.3% for pulse height spectra of 5.486 MeV α-particles emitted by 241 Am, measured directly in water. (authors)

U(SMes*)n, (n=3, 4) and Ln(SMes*)3 (Ln = La, Ce, Pr, Nd): Lanthanide(III)/actinide(III) differentiation in agostic interactions and an unprecedented eta(3) Ligation mode of the aryl-thiolate ligand, from X-ray diffraction and DFT analysis

International Nuclear Information System (INIS)

Roger, Mathieu; Barros, Noemi; Arliguie, Therese; Thuery, Pierre; Maron, Laurent; Ephritikhine, Michel

2006-01-01

Reaction of U(NEt 2 ) 4 with HS-2,4,6- t Bu 3 C 6 H 2 (HSMes*) gave U(SMes*) 3 (NEt 2 )(py) (1), whereas similar treatment of U[N(SiMe 3 )SiMe 2 CH 2 ][N(SiMe 3 ) 2 ] 2 afforded U(SMes*)[N(SiMe 3 ) 2 ] 3 (2) and U(SMes*) 3 [N(SiMe 3 ) 2 ]. The first neutral homoleptic uranium(IV) thiolate to have been crystallographically characterized, U(SMes*) 4 (4), was isolated from the reaction of U(BH 4 ) 4 and KSMes*. The first homoleptic thiolate complex of uranium(III), U(SMes*) 3 (5), was synthesized by proton-lysis of U[N(SiMe 3 ) 2 ] 3 with HSMes* in cyclohexane. The crystal structure of 5 exhibits the novel η 3 ligation mode for the aryl-thiolate ligand. Comparison of the crystal structure of 5 with those of the isomorphous lanthanide congeners Ln(SMes*) 3 (Ln) La, Ce, Pr, and Nd) indicates that the U-S, U-C ipso , and U-C ortho bond lengths are shorter than the corresponding ones in the 4f-element analogues, when taking into account the variation in the ionic radii of the metals. The distance between the uranium and the carbon atoms involved in the U center dot center dot center dot H-C ε agostic interaction of each thiolate ligand is shorter, by ∼ 0.05 angstrom, than that expected from a purely ionic bonding model. The lanthanide( III)/actinide(III) differentiation was analyzed by density functional theory (DFT). The nature of the M-S bond is shown to be ionic strongly polarized at the sulfur for M) U and ion-covalent (i.e. strongly ionic with low orbital interaction), for M) Ln. The strength of the U center dot center dot center dot H-C ε agostic interaction is proposed to be controlled by the maximization of the interaction between U + and S - under steric constraints. The η 3 ligation mode of the aryl-thiolate ligand is also obtained from DFT. (authors)

Spectroscopic investigations on the complexation of Cm(III) and Eu(III) with organic model ligands and their binding mode in human urine (in vitro); Spektroskopische Untersuchungen zur Komplexbildung von Cm(III) und Eu(III) mit organischen Modellliganden sowie ihrer chemischen Bindungsform in menschlichem Urin (in vitro)

Energy Technology Data Exchange (ETDEWEB)

Heller, Anne

2011-10-26

In case of incorporation, trivalent actinides (An(III)) and lanthanides (Ln(III)) pose a serious health risk to humans. An(III) are artificial, highly radioactive elements which are mainly produced during the nuclear fuel cycle in nuclear power plants. Via hazardous accidents or nonprofessional storage of radioactive waste, they can be released in the environment and enter the human food chain. In contrast, Ln(III) are nonradioactive, naturally occurring elements with multiple applications in technique and medicine. Consequently it is possible that humans get in contact and incorporate both, An(III) and Ln(III). Therefore, it is of particular importance to elucidate the behaviour of these elements in the human body. While macroscopic processes such as distribution, accumulation and excretion are studied quite well, knowledge about the chemical binding form (speciation) of An(III) and Ln(III) in various body fluids is still sparse. In the present work, for the first time, the speciation of Cm(III) and Eu(III) in natural human urine (in vitro) has been investigated spectroscopically and the formed complex identified. For this purpose, also basic investigations on the complex formation of Cm(III) and Eu(III) in synthetic model urine as well as with the urinary relevant, organic model ligands urea, alanine, phenylalanine, threonine and citrate have been performed and the previously unknown complex stability constants determined. Finally, all experimental results were compared to literature data and predictions calculated by thermodynamic modelling. Since both, Cm(III) and Eu(III), exhibit unique luminescence properties, particularly the suitability of time-resolved laser-induced fluorescence spectroscopy (TRLFS) could be demonstrated as a method to investigate these metal ions in untreated, complex biofluids. The results of this work provide new scientific findings on the biochemical reactions of An(III) and Ln(III) in human body fluids on a molecular scale and

Research on the chemical speciation of actinides

International Nuclear Information System (INIS)

Jung, Euo Chang; Park, K. K.; Cho, H. R.

2012-04-01

A demand for the safe and effective management of spent nuclear fuel and radioactive waste generated from nuclear power plant draws increasing attention with the growth of nuclear power industry. The objective of this project is to establish the basis of research on the actinide chemistry by using highly sensitive and advanced laser-based spectroscopic systems. Researches on the chemical speciation of actinides are prerequisite for the development of technologies related to nuclear fuel cycles, especially, such as the safe management of high level radioactive wastes and the chemical examination of irradiated nuclear fuels. For supporting these technologies, laser-based spectroscopies have been applied for the chemical speciation of actinide in aqueous solutions and the quantitative analysis of actinide isotopes in spent nuclear fuels. In this report, results on the following subjects have been summarized. Development of TRLFS technology for the chemical speciation of actinides, Development of laser-induced photo-acoustic spectroscopy (LPAS) system, Application of LIBD technology to investigate dynamic behaviors of actinides dissolution reactions, Development of nanoparticle analysis technology in groundwater using LIBD, Chemical speciation of plutonium complexes by using a LWCC system, Development of LIBS technology for the quantitative analysis of actinides, Evaluation on the chemical reactions between actinides and humic substances, Spectroscopic speciation of uranium-ligand complexes in aqueous solution, Chemical speciation of actinides adsorbed on metal oxides surfaces

A role of copper(II) ions in the enhancement of visible and near-infrared lanthanide(III) luminescence

Energy Technology Data Exchange (ETDEWEB)

Eliseeva, Svetlana V., E-mail: svetlana.eliseeva@cnrs-orleans.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Le Studium, Loire Valley Institute for Advanced Studies, 1 Rue Dupanloup, 45000 Orléans (France); Golovach, Iurii P.; Liasotskyi, Valerii S. [I.I.Mechnikov Odessa National University, 2 Dvoryanska street, 65082 Odessa (Ukraine); Antonovich, Valery P. [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine); Petoud, Stéphane, E-mail: stephane.petoud@inserm.fr [Centre de Biophysique Moléculaire CNRS UPR 4301, Rue Charles Sadron, 45071 Orléans Cedex 2 (France); Meshkova, Svetlana B., E-mail: s_meshkova@ukr.net [A.V. Bogatsky Physico-Chemical Institute of the National Academy of Sciences of Ukraine, 86 Lustdorfskaya doroga, 65080 Odessa (Ukraine)

2016-03-15

Most of the existing optical methods for Cu{sup II} detection rely on a “turn-off” approach using visible lanthanide(III) luminescence. In this work we present an innovative molecular systems where the podands bis(2-hydrazinocarbonylphenyl) ethers of ethylene glycol (L1) and diethylene glycol (L2) have been designed, synthesised and tested with an ultimate goal to create a 'turn-on' lanthanide(III)-based molecular probe for the specific detection of Cu{sup II} ions based on both visible (Tb{sup III}, Eu{sup III}) and near-infrared (Nd{sup III}, Yb{sup III}) emission. Quantum yields of the characteristic Ln{sup III} emission signals increases by at least two-orders of magnitude upon addition of Cu{sup II} into water/acetonitrile (9/1) solutions of LnL (L=L1, L2) complexes. A detailed investigation of ligand-centred photophysical properties of water/acetonitrile (9/1) solutions of CuL, GdL and GdCuL complexes revealed that the presence of Cu{sup II} ions does not significantly affect the energy positions of the singlet (32,260 cm{sup −1}) and triplet (25,640–25,970 cm{sup −1}) states, but partially or fully eliminates the singlet state quenching through an electron transfer mechanism. This effect increases the probability of intersystem crossing leading to enhanced triplet-to-singlet emission ratio and to longer triplet state lifetimes. The redox activity of hydrazine moieties and their ability to reduce Cu{sup II} to Cu{sup I} has been indicated by a qualitative assay with neocuproine. Finally, the probe demonstrates a good selectivity towards Cu{sup II} over other transition metal ions: the addition of divalent Zn{sup II}, Cd{sup II}, Pd{sup II}, Ni{sup II}, Co{sup II} or trivalent Fe{sup III}, Ga{sup III}, In{sup III} ion salts into solutions of TbL either does not affect emission intensity or increases it to a maximum of 2–3 times, while, under similar experimental conditions, the presence of Cu{sup II} results in a 20- to 30-times

NEARSOL, Aqueous Speciation and Solubility of Actinides for Waste Disposal

International Nuclear Information System (INIS)

Leach, S.J.; Pryke, D.C.

1989-01-01

A - Description of program or function: NEARSOL models the aqueous speciation and solubility of actinides under near-field conditions for disposal using a simple thermodynamic approach. B - Method of solution: The program draws information from a thermodynamic data base consisting of solubility products and complex formation constants for all known species, and standard electrode potentials, at 25 C, corrected for ionic strength effects. By minimising the free energy of the system through a series of iterations, a precipitating solid phase is predicted which limits the solubility, and the concentration of the main aqueous species are calculated as a function of pH. Initially the program evaluates only hydroxide and carbonate species, but the effect of sulphate, phosphate and fluoride anions can also be included. The program is simple to use, requiring inputs of: 1. Actinide(s); 2. pH range; 3. Ionic strength; 4. Redox conditions; 5. Ligand concentrations. Functions are included to calculate the distribution of the protonated and un-protonated forms of carbonate and phosphate and the value of Eh as a function of pH under disposal conditions as required. The program can further evaluate the role of free calcium ions. C - Restrictions on the complexity of the problem: None

Molecular cluster theory of chemical bonding in actinide oxide

International Nuclear Information System (INIS)

Ellis, D.E.; Gubanov, V.A.; Rosen, A.

1978-01-01

The electronic structure of actinide monoxides AcO and dioxides AcO 2 , where Ac = Th, U, Np, Pu, Am, Cm and Bk has been studied by molecular cluster methods based on the first-principles one-electron local density theory. Molecular orbitals for nearest neighbor clusters AcO 10- 6 and AcO 12- 8 representative of monoxide and dioxide lattices were obtained using non-relativistic spin-restricted and spin-polarized Hartree-Fock-Slater models for the entire series. Fully relativistic Dirac-Slater calculations were performed for ThO, UO and NpO in order to explore magnitude of spin-orbit splittings and level shifts in valence structure. Self-consistent iterations were carried out for NpO, in which the NpO 6 cluster was embedded in the molecular field of the solid. Finally, a ''moment polarized'' model which combines both spin-polarization and relativistic effects in a consistent fashion was applied to the NpO system. Covalent mixing of oxygen 2p and Ac 5f orbitals was found to increase rapidly across the actinide series; metal s,p,d covalency was found to be nearly constant. Mulliken atomic population analysis of cluster eigenvectors shows that free-ion crystal field models are unreliable, except for the light actinides. X-ray photoelectron line shapes have been calculated and are found to compare rather well with experimental data on the dioxides

Safe actinide disposition in molten salt reactors

International Nuclear Information System (INIS)

Gat, U.

1997-01-01

Safe molten salt reactors (MSR) can readily accommodate the burning of all fissile actinides. Only minor compromises associated with plutonium are required. The MSRs can dispose safely of actinides and long lived isotopes to result in safer and simpler waste. Disposing of actinides in MSRs does increase the source term of a safety optimized MSR. It is concluded that the burning and transmutation of actinides in MSRs can be done in a safe manner. Development is needed for the processing to handle and separate the actinides. Calculations are needed to establish the neutron economy and the fuel management. 9 refs

The reprocessing-recycling of spent nuclear fuel. Actinides separation - Application to wastes management; Le traitement-recyclage du combustible nucleaire use. La separation des actinides - Application a la gestion des dechets

Energy Technology Data Exchange (ETDEWEB)

NONE

2008-07-01

After its use in the reactor, the spent fuel still contains lot of recoverable material for an energetic use (uranium, plutonium), but also fission products and minor actinides which represent the residues of nuclear reactions. The reprocessing-recycling of the spent fuel, as it is performed in France, implies the chemical separation of these materials. The development and the industrial implementation of this separation process represent a major contribution of the French science and technology. The reprocessing-recycling allows a good management of nuclear wastes and a significant saving of fissile materials. With the recent spectacular rise of uranium prices, this process will become indispensable with the development of the next generation of fast neutron reactors. This book takes stock of the present and future variants of the chemical process used for the reprocessing of spent fuels. It describes the researches in progress and presents the stakes and recent results obtained by the CEA. content: the separation of actinides, a key factor for a sustainable nuclear energy; the actinides, a discovery of the 20. century; the radionuclides in nuclear fuels; the aquo ions of actinides; some redox properties of actinides; some complexing properties of actinide cations; general considerations about treatment processes; some characteristics of nuclear fuels in relation with their reprocessing; technical goals and specific constraints of the PUREX process; front-end operations of the PUREX process; separation and purification operations of the PUREX process; elaboration of finite products in the framework of the PUREX process; management and treatment of liquid effluents; solid wastes of the PUREX process; towards a joint management of uranium and plutonium: the COEX{sup TM} process; technical options of treatment and recycling techniques; the fuels of generation IV reactors; front-end treatment processes of advanced fuels; hydrometallurgical processes for future fuel

QSAR studies of multidentate nitrogen ligands used in lanthanide and actinide extraction processes

International Nuclear Information System (INIS)

Drew, Michael G.B.; Hudson, Michael J.; Youngs, Tristan G.A.

2004-01-01

Quantitative structure activity relationships (QSARs) have been developed to optimise the choice of nitrogen heterocyclic molecules that can be used to separate the minor actinides such as americium(III) from europium(III) in the aqueous PUREX raffinate of nuclear waste. Experimental data on distribution coefficients and separation factors (SFs) for 47 such ligands have been obtained and show SF values ranging from 0.61 to 100. The ligands were divided into a training set of 36 molecules to develop the QSAR and a test set of 11 molecules to validate the QSAR. Over 1500 molecular descriptors were calculated for each heterocycle and the Genetic Algorithm was used to select the most appropriate for use in multiple regression equations. Equations were developed fitting the separation factors to 6-8 molecular descriptors which gave r 2 values of >0.8 for the training set and values of >0.7 for the test set, thus showing good predictive quality. The descriptors used in the equations were primarily electronic and steric. These equations can be used to predict the separation factors of nitrogen heterocycles not yet synthesised and/or tested and hence obtain the most efficient ligands for lanthanide and actinide separation

Lanthanide and actinide complexation studies with tetradentate 'N' donor ligands

International Nuclear Information System (INIS)

Bhattacharyya, A.; Mohapatra, M.; Mohapatra, P.K.; Rawat, N.; Tomar, B.S.; Gadly, T.; Ghosh, S.K.; Manna, D.; Ghanty, T.K.

2014-01-01

Because of their similar charge and chemical behaviour separation of trivalent actinides and lanthanides is an important and challenging task in nuclear fuel cycle. Soft (S,N) donor ligands show selectivity towards the trivalent actinides over the lanthanides. Out of various 'N' donor ligands studied, bis(1,2,4)triazinyl bipyridine (BTBP) and bis(1,2,4)triazinyl phenanthroline (BTPhen) were found to be most promising. In order to understand the separation behaviour of these ligands, their complexation studies with these 'f' block elements are essential. In the present work, complexation studies of various lanthanide ions (La 3+ , Eu 3+ and Er 3+ ) was studied with ethyl derivatives of BTBP (C 2 BTBP) and BTBPhen (C 2 BTPhen) and pentyl derivative of BTBP (C 5 BTBP) in acetonitrile medium using UV-Vis spectrophotometry, fluorescence spectroscopy and solution calorimetry. Computational studies were also carried out to understand the experimental results

Liquid-liquid extraction of actinides by means of dibutil-N, N-diethylcarbamylphosphanate (DBDECP)

International Nuclear Information System (INIS)

Spezzano, P.; Giacomelli, R.; Sarzanini, C.; Volpe, P.; Benzi, P.

1988-01-01

The extraction of Th(IV), U(VI), Pu(IV), Am(III) and Cm(III) by dibutyl-N, N-diethilcarbamoylphosphonate (DBDECP) from notric, hydrochloric and perchloric acid solutions has been studies as a function of a number of parameters. The effect of size and structure of the extractant molecules has been investigated for lower homologues of carbamoyphosphonate. After evaluating the effect of the diluent, the extraction of inorganic acid HNO 3 , HCl and HClO 4 and the dipendence of the distribution ratios of the actinides from organic extractant concentration and aqueous acid concentration has been studied for the DBDECP-xilene system

Monazite-type ceramics for conditioning of minor actinides. Structural characterization and properties

Energy Technology Data Exchange (ETDEWEB)

Babelot, Carole

2013-07-01

essential parameter is their resistance to radiation. The damage created by the recoils accompanying alpha-decay can be simulated on ceramic matrices. Preliminary experiments are realized by means of ion bombardment. Kr{sup 2+} ions are implanted in La-monazite-type pellets, and the effects on the LaPO{sub 4} structure resulting from the Raman spectroscopy are poor. On a laboratory scale, the promising characteristics of the monazite mineral are found again in the synthetic phosphate. In particular, the doping of actinide surrogates is successful and the corrosion tests under repository conditions show a good resistance of the samples. The results achieved in this work confirm that among other favorable ceramics (e.g. pyrochlore) the ''monazite-route'' has to be further pursued regarding the research on the conditioning of MA.

Mechanistic role of citric acid in the sorption of Eu(III) at titania - water interface

International Nuclear Information System (INIS)

Kumar, Sumit; Kasar, Sharayu; Tomar, B.S.

2014-01-01

In view of the deep underground disposal strategy of nuclear high level waste, environmental behavior of long lived radionuclides, such as, trivalent actinides Am(III) and Cm(III), attract significant scientific attention. Interaction of trivalent actinides with anatase (TiO 2 ) in presence of citric acid has been investigated in the present work using Eu(III) batch sorption studies and the role of citric acid in influencing sorption of Eu(III) on anatase was delineated using surface speciation of Eu(III) and citric acid on anatase surface. Results from ATR-FTIR spectroscopic study have been invoked to determine the binding of citric acid on anatase surface. Eu(III) sorption on anatase increases sharply to quantitative value over pH 3- 6 and remains at 100% upto pH 10. In presence of citric acid, there is no change in Eu(III) sorption in the pH range 2-5 whereas significant lowering in Eu(III) sorption percentage was obtained in the pH range 5-8. Above pH 8 the sorption percentage reached quantitative value

Actinides burnup in a sodium fast reactor

Energy Technology Data Exchange (ETDEWEB)

Ramirez S, J. R.; Pineda A, R.; Martinez C, E.; Alonso, G., E-mail: ramon.ramirez@inin.gob.mx [ININ, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico)

2017-09-15

The burnup of actinides in a nuclear reactor is been proposed as part of an advanced nuclear fuel cycle, this process would close the fuel cycle recycling some of the radioactive material produced in the open nuclear fuel cycle. These actinides are found in the spent nuclear fuel from nuclear power reactors at the end of their burnup in the reactor. Previous studies of actinides recycling in thermal reactors show that would be possible reduce the amounts of actinides at least in 50% of the recycled amounts. in this work, the amounts of actinides that can be burned in a fast reactor is calculated, very interesting results surge from the calculations, first, the amounts of actinides generated by the fuel is higher than for thermal fuel and the composition of the actinides vector is different as in fuel for thermal reactor the main isotope is the {sup 237}Np in the fuel for fast reactor the main isotope is the {sup 241}Am, finally it is concluded that the fast reactor, also generates important amounts of waste. (Author)

First light on 3d photoionization of multiply charged xenon ions: a new photon-ion merged beam setup at PETRA III

International Nuclear Information System (INIS)

Ricz, S; Schippers, S; Buhr, T; Holste, K; Jr, A Borovik; Hellhund, J; Schäfer, H-J; Schury, D; Klumpp, S; Mertens, K; Martins, M; Flesch, R; Ulrich, G; Rühl, E; Lower, J; Jahnke, T; Metz, D; Schmidt, L; Schöffler, M; Williams, J B

2014-01-01

A photon-ion merged beam endstation has been set up at the variable polarization XUV-beamline P04 of PETRA III in Hamburg. In a commissioning experiment first results could be obtained for multiple photoionization of Xe q+ ions (q = 1,2,..,5) at photon energies around the 3d ionization threshold.

Burning actinides in very hard spectrum reactors

International Nuclear Information System (INIS)

Robinson, A.H.; Shirley, G.W.; Prichard, A.W.; Trapp, T.J.

1978-01-01

The major unresolved problem in the nuclear industry is the ultimate disposition of the waste products of light water reactors. The study demonstrates the feasibility of designing a very hard spectrum actinide burner reactor (ABR). A 1100 MW/sub t/ ABR design fueled entirely with actinides reprocessed from light water reactor (LWR) wastes is proposed as both an ultimate disposal mechanism for actinides and a means of concurrently producing usable power. Actinides from discharged ABR fuel are recycled to the ABR while fission products are routed to a permanent repository. As an integral part of a large energy park, each such ABR would dispose of the waste actinides from 2 LWRs

Solvent extraction separations of trivalent lanthanide and actinide ions using an aqueous aminomethanediphosphonic acid

International Nuclear Information System (INIS)

Jensen, M. P.

1998-01-01

The possibility of separating the trivalent lanthanides, represented by EU 3+ , and actinides, represented by Cf 3+ , using HDEHP in toluene and an aqueous phase containing N-piperidinomethane-1,1-diphosphotic acid, PMDPA, has been investigated. This modified aqueous phase offers potential advantages over the diethylenetriaminepentaacetic acid based TALSPEAK process because of the improved complexation properties of PMDPA in acidic solutions, and the ability to decompose PMDPA before disposal. Extraction experiments were conducted at 25 C in 2 M NaClO 4 between -log [H + ] 1 and 2. The studies enabled us to derive the aqueous phase speciation, the stability constants of the aqueous complexes, and the Cf/Eu separation factors. Despite the presence of an amino group in PMDPA that should favor the retention of the actinides in the aqueous phase, the Cf/Eu separation factors are near unity under the conditions studied

Actinide separative chemistry

International Nuclear Information System (INIS)

Boullis, B.

2004-01-01

Actinide separative chemistry has focused very heavy work during the last decades. The main was nuclear spent fuel reprocessing: solvent extraction processes appeared quickly a suitable, an efficient way to recover major actinides (uranium and plutonium), and an extensive research, concerning both process chemistry and chemical engineering technologies, allowed the industrial development in this field. We can observe for about half a century a succession of Purex plants which, if based on the same initial discovery (i.e. the outstanding properties of a molecule, the famous TBP), present huge improvements at each step, for a large part due to an increased mastery of the mechanisms involved. And actinide separation should still focus R and D in the near future: there is a real, an important need for this, even if reprocessing may appear as a mature industry. We can present three main reasons for this. First, actinide recycling appear as a key-issue for future nuclear fuel cycles, both for waste management optimization and for conservation of natural resource; and the need concerns not only major actinide but also so-called minor ones, thus enlarging the scope of the investigation. Second, extraction processes are not well mastered at microscopic scale: there is a real, great lack in fundamental knowledge, useful or even necessary for process optimization (for instance, how to design the best extracting molecule, taken into account the several notifications and constraints, from selectivity to radiolytic resistivity?); and such a need for a real optimization is to be more accurate with the search of always cheaper, cleaner processes. And then, there is room too for exploratory research, on new concepts-perhaps for processing quite new fuels- which could appear attractive and justify further developments to be properly assessed: pyro-processes first, but also others, like chemistry in 'extreme' or 'unusual' conditions (supercritical solvents, sono-chemistry, could be

Actinides integral measurements on FCA assemblies

International Nuclear Information System (INIS)

Mukaiyama, Takehiko; Okajima, Shigeaki

1984-01-01

Actinide integral measurements were performed on eight assemblies of FCA where neutron energy spectra were shifted systematically from soft to hard in order to evaluate and modify the nuclear cross section data of major actinides. Experimental values on actinide fission rates and sample reactivity worths are compared with the calculated values using JENDL-2 and ENDF/B-V (or IV) data sets. (author)

The reprocessing-recycling of spent nuclear fuel. Actinides separation - Application to wastes management

International Nuclear Information System (INIS)

2008-01-01

After its use in the reactor, the spent fuel still contains lot of recoverable material for an energetic use (uranium, plutonium), but also fission products and minor actinides which represent the residues of nuclear reactions. The reprocessing-recycling of the spent fuel, as it is performed in France, implies the chemical separation of these materials. The development and the industrial implementation of this separation process represent a major contribution of the French science and technology. The reprocessing-recycling allows a good management of nuclear wastes and a significant saving of fissile materials. With the recent spectacular rise of uranium prices, this process will become indispensable with the development of the next generation of fast neutron reactors. This book takes stock of the present and future variants of the chemical process used for the reprocessing of spent fuels. It describes the researches in progress and presents the stakes and recent results obtained by the CEA. content: the separation of actinides, a key factor for a sustainable nuclear energy; the actinides, a discovery of the 20. century; the radionuclides in nuclear fuels; the aquo ions of actinides; some redox properties of actinides; some complexing properties of actinide cations; general considerations about treatment processes; some characteristics of nuclear fuels in relation with their reprocessing; technical goals and specific constraints of the PUREX process; front-end operations of the PUREX process; separation and purification operations of the PUREX process; elaboration of finite products in the framework of the PUREX process; management and treatment of liquid effluents; solid wastes of the PUREX process; towards a joint management of uranium and plutonium: the COEX TM process; technical options of treatment and recycling techniques; the fuels of generation IV reactors; front-end treatment processes of advanced fuels; hydrometallurgical processes for future fuel cycles

Theoretical study of the structure and the reactivity of lanthanides and actinides complexes: Activation of small molecules

International Nuclear Information System (INIS)

Castro, Ludovic

2012-01-01

This PhD thesis presents a theoretical study of the structure and the reactivity of organometallic complexes of lanthanides and actinides at the DFT level. After a general introduction of the methods of theoretical chemistry used for the modelling of organometallic reactivity, a study of the participation of 5f electrons in uranium(IV) reactivity is presented. The results show that the large core ECP can be used safely in order to treat the actinide and so that 5f electrons can be treated implicitly. Then, the reactivity of uranium(III) complexes with CO 2 and other analogous molecules is studied via multiple examples from the literature. These studies show that the steric nature of the ligands is very important and controls the reactivity. This study is then extended to samarium(II) complex. Eventually, the reactivity of a hydride complex of cerium(III) with MeOSO 2 Me is investigated and theoretical results are compared with experimental observations. (author) [fr

Energy level schemes of f{sup N} electronic configurations for the di-, tri-, and tetravalent lanthanides and actinides in a free state

Energy Technology Data Exchange (ETDEWEB)

Ma, C.-G. [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Brik, M.G., E-mail: mikhail.brik@ut.ee [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Institute of Physics, University of Tartu, Ravila 14C, Tartu 50411 (Estonia); Institute of Physics, Jan Dlugosz University, Armii Krajowej 13/15, PL-42200 Czestochowa (Poland); Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland); Liu, D.-X.; Feng, B.; Tian, Ya [College of Sciences, Chongqing University of Posts and Telecommunications, Chongqing 400065 (China); Suchocki, A. [Institute of Physics, Polish Academy of Sciences, Al. Lotników 32/46, 02-668 Warsaw (Poland)

2016-02-15

The energy level diagrams are theoretically constructed for the di-, tri-, tetravalent lanthanide and actinide ions, using the Hartree–Fock calculated parameters of the Coulomb and spin–orbit interactions within f{sup N} (N=1…13) electron configurations. These diagrams are analogous to Dieke's diagram, which was obtained experimentally. They can be used for an analysis of the optical spectra of all considered groups of ions in various environments. Systematic variation of some prominent energy levels (especially those ones with a potential for emission transitions) along the isoelectronic 4f/5f ions is considered. - Highlights: • Energy level schemes for di-, tri, tetravalent lanthanides/actinides are calculated. • Systematic variation of the characteristic energy levels across the series is considered. • Potentially interesting emission transitions are identified.

Actinide burning and waste disposal

Energy Technology Data Exchange (ETDEWEB)

Pigford, T H [University of California, Berkeley, CA (United States)

1990-07-01

Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

Actinide burning and waste disposal

International Nuclear Information System (INIS)

Pigford, T.H.

1990-01-01

Here we review technical and economic features of a new proposal for a synergistic waste-management system involving reprocessing the spent fuel otherwise destined for a U.S. high-level waste repository and transmuting the recovered actinides in a fast reactor. The proposal would require a U.S. fuel reprocessing plant, capable of recovering and recycling all actinides, including neptunium americium, and curium, from LWR spent fuel, at recoveries of 99.9% to 99.999%. The recovered transuranics would fuel the annual introduction of 14 GWe of actinide-burning liquid-metal fast reactors (ALMRs), beginning in the period 2005 to 2012. The new ALMRs would be accompanied by pyrochemical reprocessing facilities to recover and recycle all actinides from discharged ALMR fuel. By the year 2045 all of the LWR spent fuel now destined f a geologic repository would be reprocessed. Costs of constructing and operating these new reprocessing and reactor facilities would be borne by U.S. industry, from the sale of electrical energy produced. The ALMR program expects that ALMRs that burn actinides from LWR spent fuel will be more economical power producers than LWRs as early as 2005 to 2012, so that they can be prudently selected by electric utility companies for new construction of nuclear power plants in that era. Some leaders of DOE and its contractors argue that recovering actinides from spent fuel waste and burning them in fast reactors would reduce the life of the remaining waste to about 200-300 years, instead of 00,000 years. The waste could then be stored above ground until it dies out. Some argue that no geologic repositories would be needed. The current view expressed within the ALMR program is that actinide recycle technology would not replace the need for a geologic repository, but that removing actinides from the waste for even the first repository would simplify design and licensing of that repository. A second geologic repository would not be needed. Waste now planned

Mass spectrometric studies of the complexing behaviour of actinide ions in solution

International Nuclear Information System (INIS)

Steppert, Michael

2012-01-01

As the long-term radiotoxicity of spent nuclear fuel is governed by Plutonium and the Minor Actinides, these elements are focussed on for investigations in the framework of safety assessment for nuclear waste repositories. To shed more light on the selectivity of the partitioning ligands BTP and BTBP towards the extraction of trivalent actinides, the complexes these ligands form with lanthanides in octanolic solution were characterized. The differences in the extraction efficiencies among the different lanthanides were traced back to the varying preferential formation of Ln(BTP)3 complexes, depending on the ionic radius of the lanthanides. Additionally it was shown that depending on the sterical demand of BTBP ligands nitrate anions coordinate in the first coordination shell of Eu(BTBP)2-complexes. As the behavior of Plutonium under geochemical conditions is of particular interest for the safety assessment of potential nuclear waste repositories, the second part of the thesis focuses on the hydrolysis and colloid formation behavior of aqueous Plutonium solutions. The solution species of Zirconium(IV) as analogue for Plutonium(IV) as well as of Uranium(VI) and Plutonium(VI) were characterized and quantified by means of electrospray ionization mass spectrometry. Moreover the colloid-induced reduction of Pu(V) to Pu(IV) and the subsequent formation of colloidal species was investigated. [de

Radiochemical study of the sorption of iodate ions on iron(III) hydroxide precipitate

International Nuclear Information System (INIS)

Music, S.; Sipalo-Zuljevic, J.; Wolf, R.H.H.

1980-01-01

The sorption of iodate ions on iron(III) hydroxide in dependence on the pH, the aging time of the precipitate and the duration of the contact between the sorbate and the sorbent have been studied. Na 131 IO 3 was used as a radioactive indicator. The sorption mechanism has been discussed in terms of electrostatic and ion-exchange processes at the solid/liquid interface. (author)

Some aspects of the extraction separation of actinides by macrocyclic crown compounds

International Nuclear Information System (INIS)

Kumar, Anil; Singh, R.K.; Bajpai, D.D.; Shukla, J.P.

1994-01-01

Selective and effective extraction-separation of U(VI) and Pu(IV) from aqueous nitric acid media by several crown ethers have been investigated in detail. The critical study of various parameters namely aqueous phase acidity, reagent concentration, diluent, period of equilibration, aqueous to organic phase ratio, strippant and diverse ions, have established the conditions for their optimum extraction. Influence of the introduction of sulfur into a crown ether ring forming a mixed sulfur-oxygen containing macrohetrocycle for improved extraction of actinides is also studied. The species extracted appear to be of ion-pair type, UO 2 (CE) 2+ .2NO 3- and Pu(CE) 2 4+ .4NO 3- formed with U(VI) and Pu(IV), respectively. The apparent extraction equilibrium constant, log Kex, into toluene by DC18C6 with U(VI) is 0.44 and 4.44 for Pu(IV). Recovery of actinides from loaded macrocycles is easily accomplished using dilute oxalic acid, perchloric acid, sulphuric acid or sodium carbonate as the strippants. The lack of interference from even appreciable amounts of possible fission product contaminants is a notable feature of this separation procedure. (author). 20 refs., 6 figs., 6 tabs

Catalytic Organic Transformations Mediated by Actinide Complexes

Directory of Open Access Journals (Sweden)

Isabell S. R. Karmel

2015-10-01

Full Text Available This review article presents the development of organoactinides and actinide coordination complexes as catalysts for homogeneous organic transformations. This chapter introduces the basic principles of actinide catalysis and deals with the historic development of actinide complexes in catalytic processes. The application of organoactinides in homogeneous catalysis is exemplified in the hydroelementation reactions, such as the hydroamination, hydrosilylation, hydroalkoxylation and hydrothiolation of alkynes. Additionally, the use of actinide coordination complexes for the catalytic polymerization of α-olefins and the ring opening polymerization of cyclic esters is presented. The last part of this review article highlights novel catalytic transformations mediated by actinide compounds and gives an outlook to the further potential of this field.

Burn of actinides in MOX fuel cells

International Nuclear Information System (INIS)

Martinez C, E.; Ramirez S, J. R.; Alonso V, G.

2017-09-01

The spent fuel from nuclear reactors is stored temporarily in dry repositories in many countries of the world. However, the main problem of spent fuel, which is its high radio-toxicity in the long term, is not solved. A new strategy is required to close the nuclear fuel cycle and for the sustain ability of nuclear power generation, this strategy could be the recycling of plutonium to obtain more energy and recycle the actinides generated during the irradiation of the fuel to transmute them in less radioactive radionuclides. In this work we evaluate the quantities of actinides generated in different fuels and the quantities of actinides that are generated after their recycling in a thermal reactor. First, we make a reference calculation with a regular enriched uranium fuel, and then is changed to a MOX fuel, varying the plutonium concentrations and determining the quantities of actinides generated. Finally, different amounts of actinides are introduced into a new fuel and the amount of actinides generated at the end of the fuel burn is calculated, in order to determine the reduction of minor actinides obtained. The results show that if the concentration of plutonium in the fuel is high, then the production of minor actinides is also high. The calculations were made using the cell code CASMO-4 and the results obtained are shown in section 6 of this work. (Author)

Gadolinium(III) ion selective sensor using a new synthesized Schiff's base as a sensing material

International Nuclear Information System (INIS)

Zamani, Hassan Ali; Mohammadhosseini, Majid; Haji-Mohammadrezazadeh, Saeed; Faridbod, Farnoush; Ganjali, Mohammad Reza; Meghdadi, Soraia; Davoodnia, Abolghasem

2012-01-01

According to a solution study which showed a selective complexation between N,N′-bis(methylsalicylidene)-2-aminobenzylamine (MSAB) and gadolinium ions, MSAB was used as a sensing element in construction of a gadolinium(III) ion selective electrode. Acetophenon (AP) was used as solvent mediator and sodium tetraphenyl borate (NaTPB) as an anion excluder. The electrode showed a good selectivity towards Gd(III) ions over a wide variety of cations tested. The constructed sensor displayed a Nernstian behavior (19.7 ± 0.3 mV/decade) in the concentration range of 1.0 × 10 −6 to 1.0 × 10 −2 mol L −1 with detection limit of 5.0 × 10 −7 mol L −1 and a short response time ( 3+ –PVC membrane sensor based on an ion carrier as sensing material is introduced. ► This technique is very simple and it's not necessary to use sophisticated equipment. ► This sensor shows good selectivity against other metal ions.

Minor actinide transmutation - a waste management option

International Nuclear Information System (INIS)

Koch, L.

1986-01-01

The incentive to recycle minor actinides results from the reduction of the long-term α-radiological risk rather than from a better utilization of the uranium resources. Nevertheless, the gain in generated electricity by minor actinide transmutation in a fast breeder reactor can compensate for the costs of their recovery and make-up into fuel elements. Different recycling options of minor actinides are discussed: transmutation in liquid metal fast breeder reactors (LMFBRs) is possible as long as plutonium is not recycled in light water reactors (LWRs). In this case a minor actinide burner with fuel of different composition has to be introduced. The development of appropriate minor actinide fuels and their properties are described. The irradiation experiments underway or planned are summarized. A review of minor actinide partitioning from the PUREX waste stream is given. From the present constraints of LMFBR technology a reduction of the long-term α-radiological risk by a factor of 200 is deduced relative to that from the direct storage of spent LWR fuel. Though the present accumulation of minor actinides is low, nuclear transmutation may be needed when nuclear energy production has grown. (orig.)

The development of a laser-induced photoacoustic facility for actinide speciation

International Nuclear Information System (INIS)

Ewart, F.T.; McMillan, J.W.; Pollard, P.M.; Thomason, H.P.; Liezers, M.

1987-09-01

A laser induced photoacoustic spectroscopy (LIPAS) facility has been developed at Harwell to measure actinide species in solution with the minimal disturbance of the species equilibria. The novel true dual beam system, which is based on an excimer laser driven dye laser and optical cells mounted on piezoelectric detectors, has high sensitivity and stability, and is capable of detecting Am(III) at ca 10 -8 M and Np(IV), (V) and (VI) at ca 10 -7 M. Samples can be measured in an inert atmosphere glove box which helps to maintain the anaerobic conditions expected in deep waste repositories. To date, LIPAS has been used to measure actinide species directly in solutions from waste programmes and to observe americium and neptunium species in solutions of varying Eh, pH and carbonate concentration. The information gained is being used to validate the data used in the geochemical/thermodynamic codes used to predict possible radionuclide species within a radioactive waste repository. (author)

The development of a laser-induced photoacoustic facility for actinide speciation

International Nuclear Information System (INIS)

Ewart, F.T.; McMillan, J.W.; Thomason, H.P.; Liezers, M.; Pollard, P.M.

1988-02-01

A laser induced photoacoustic spectroscopy (LIPAS) facility has been developed at Harwell to measure actinide species in solution with the minimal disturbance of the species equilibria. The novel true dual beam system, which is based on an excimer laser driven dye laser and optical cells mounted on piezoelectric detectors, has high sensitivity and stability, and is capable of detecting Am(III) at ca 10 -8 M and Np(IV), (V) and (VI) at ca 10 -7 M. Samples can be measured in an inert atmosphere glove box which helps to maintain the anaerobic conditions expected in deep waste repositories. To date, LIPAS has been used to measure actinide species directly in solutions from waste programmes and to observe americium and neptunium species in solutions of varying Eh, pH and carbonate concentration. The information gained is being used to validate the data used in the geochemical/thermodynamic codes used to predict possible radionuclide species within a radioactive waste repository. (author)

Separation of actinides and lanthanides from acidic nuclear wastes by supported liquid membranes

International Nuclear Information System (INIS)

Danesi, P.R.; Chiarizia, R.; Rickert, P.; Horwitz, E.P.

1985-01-01

Supported liquid membranes, SLM, consisting of a solution of 0.25 M octyl(phenyl)-N,N-diisobutylcarbamoylmethylphosphine oxide (CMPO) and 0.75 M tributylphosphate (TBP) in decalin absorbed on thin microporous polypropylene supports, have been studied for their ability to perform selective separations and concentrations of actinide and lanthanide ions from synthetic acidic nuclear wastes. The permeability coefficients of selected actinides (Am, Pu, U, Np) and of some of the other major components of the wastes have been measured using SLMs in flat-sheet and hollow-fiber configurations. The results have shown that with the thin (25 μm) flat-sheet SLMs, using Celgard 2500 as support, the membrane permeation process is mainly controlled by the rate of diffusion through the aqueous boundary layers. With the thicker (430 μm) hollow-fiber SLMs, using Accurel hollow-fibers as support, the membrane permeation process is controlled by the rate of diffusion through both the SLM and the aqueous boundary layers. Hollow-fibers SLMs exhibited lower permeability coefficients and longer life-times. The experiments have shown that the actinides can be very efficiently removed from the synthetic waste solutions to the point that the resulting solution could be considered a non-transuranic waste (less than 100 mCi/g of disposed form). The work has demonstrated that actinide removal from synthetic waste solutions is a feasible chemical process at the laboratory scale level

Magnetic Properties of linear chain compounds formed by lanthanide (III) ions and nitronyl-nitroxide radicals

Energy Technology Data Exchange (ETDEWEB)

Benelli, C.; Caneschi, A.; Gatteschi, D.; Pardi, L. (Florence Univ. (IT)); Rey, P. (CEA Centre d' Etudes Nucleaires de Grenoble, 38 (FR). Dept. de Recherche Fondamentale)

1988-12-01

The magnetic properties of novel linear chain compounds containing lanthanide (III) ions (gadolinium, europium) coupled to stable nitronyl-nitroxide radicals are reported. The metal ions and the radicals are regularly alternating along the chain. The magnetic behaviors appears to be dominated by antiferromagnetic interactions between the radicals.

Magnetic Properties of linear chain compounds formed by lanthanide (III) ions and nitronyl-nitroxide radicals

International Nuclear Information System (INIS)

Benelli, C.; Caneschi, A.; Gatteschi, D.; Pardi, L.; Rey, P.

1988-01-01

The magnetic properties of novel linear chain compounds containing lanthanide (III) ions (gadolinium, europium) coupled to stable nitronyl-nitroxide radicals are reported. The metal ions and the radicals are regularly alternating along the chain. The magnetic behaviors appears to be dominated by antiferromagnetic interactions between the radicals

Overall assessment of actinide partitioning and transmutation for waste management purposes

International Nuclear Information System (INIS)

Blomeke, J.O.; Croff, A.G.; Finney, B.C.; Tedder, D.W.

1980-01-01

A program to establish the technical feasibility and incentives for partitioning (i.e., recovering) actinides from fuel cycle wastes and then transmuting them in power reactors to shorter-lived or stable nuclides has recently been concluded at the Oak Ridge National Laboratory. The feasibility was established by experimentally investigating the reduction that can be practicably achieved in the actinide content of the wastes sent to a geologic repository, and the incentives for implementing this concept were defined by determining the incremental costs, risks, and benefits. Eight US Department of Energy laboratories and three private companies participated in the program over its 3-year duration. A reference fuel cycle was chosen based on a self-generated plutonium recycle PWR, and chemical flowsheets based on solvent extraction and ion-exchange techniques were generated that have the potential to reduce actinides in fuel fabrication and reprocessing plant wastes to less than 0.25% of those in the spent fuel. Waste treatment facilities utilizing these flowsheets were designed conceptually, and their costs were estimated. Finally, the short-term (contemporary) risks from fuel cycle operations and long-term (future) risks from deep geologic disposal of the wastes were estimated for cases with and without partitioning and transmutation. It was concluded that, while both actinide partitioning from wastes and transmutation in power reactors appear to be feasible using currently identified and studied technology, implementation of this concept cannot be justified because of the small long-term benefits and substantially increased costs of the concept

Interaction of Cr (III), Ni (II), Pb (II) with DTPA complexes of essential metal ions

International Nuclear Information System (INIS)

Gulzar, S.; Zahida; Maqsood, T.; Naqvi, R.R.

2002-01-01

With the increase of anthropogenic activities in the environment, heavy metal toxicity (Chromium, Nickel and Lead) is more common now. DTPA (diethylene triamine pentaacetic acid) a polyamino carboxylic acid is widely used to form hydrophilic and stable complexes with most of the metal ions. In this spectrophotometric study, concentration of Cr(III), Ni(II) and Pb(II) (toxic metal ions) exchanged with Fe(III), Zn(II) and Ca(II) from their DTPA complexes were estimated at pH 4,7 and 9. Concentration of added metal was varied from 1-4 times to that of complexed metal. (author)

Thermodynamics of the extraction of Eu(III) and Am(III) with synergistic mixtures of thenoyltrifluoroacetone and a linear polyether

International Nuclear Information System (INIS)

Ensor, D.D.; Shah, A.H.

1983-01-01

The extractions of trivalent lanthanides and actinides by synergistic mixtures of thenoyltrifluoroacetone (HTTA) and a variety of neutral oxygen donors are well documented. The large increase in the extent of extraction of the metal ion into the organic phase is believed to occur by one of three possible mechanisms. The first involves the direct replacement of residual waters of hydration on the metal by the neutral donor. In the second proposed mechanism, the residual waters remain attached to the metal and the neutral oxygen donor hydrogen bond to the complex through the waters. The final mechanism assumes the complex is not hydrated and the addition of the neutral donor requires the metal to increase its coordination number. A recent review of the synergistic effect showed that the proper interpretation of the mechanism requires the measurement of ΔH and ΔS for the reaction. The synergistic capabilities of a linear polyether, 1,13-bis-[8-quinolyl]-1,4,7,10,13-pentaoxotridecane (K-5), in combination with HTTA to extract Am(III) and Eu(III) have been recently reported by the investigators. The presence of the K-5 in the organic phase not only increased the extraction of the trivalent metals, but also showed a preference for Am(III) over Eu(III). This result was surprising since most neutral donors do not alter the selectivity of HTTA. In an effort to better understand the synergistic mechanism of the K-5/HTTA system, the thermodynamic parameters have been measured by a temperature variation method, and results are reported in this paper. 7 references

Investigation of extraction of actinyl ions with inorganic ligands Pt. 1

International Nuclear Information System (INIS)

Fucks, L.; Lis, S.; Fidelis, I.

1979-01-01

Extraction coefficients (D) of hexavalent actinide ions have been determined by extraction chromatography, utilizing the selectivity of the TBP - HNO 3 system towards oxidation states. Plots logD against nitric acid concentration and logD against the atomic number of actinides show the decrease of extractability with Z, and a distinctly smaller difference between the extractability of uranyl and neptunyl than that of neptunyl and plutonyl ions. This latter fact is connected with the double-double effect. (A.L.)

Plutonium Management, Minor Actinides Partitioning and Transmutation R and D in France

International Nuclear Information System (INIS)

Cavedon, Jean-Marc; Courtois, Charles

2003-01-01

Jean-Marc Cavedon (CEA, France) then presented the developments concerning Plutonium management and minor actinides P and T research and development in France. By the 1991 law on high-level long-lived radioactive waste a research programme was launched in the areas: (i) geological disposal, (ii) conditioning and long-term storage, and (iii) radiotoxicity reduction by P and T. The results of the work in these areas will be presented to the French Government and Parliament in 2006. The control of Plutonium stocks generated by the French PWRs is proposed to increase Plutonium consumption in reactors and minimise radioactive waste production, and requires the recycling of actinides, especially Plutonium. In the long term, CEA intends to develop a new technology based on gas cooled reactors and their associated fuel cycle, including multiple recycling of Plutonium. The advantages of this development consist in the optimisation of the use of natural resources and the concentration of Plutonium in limited quantities of fuel rods. If needed, the minor actinides could also be recycled. The planned CEA developments depend on new fuel types and will lead to novel waste types (light glasses) with a reduction of long-term radiotoxicity. Radiotoxicity reductions by a factor of 3 to 5 are expected for Plutonium recycling scenarios, and by up to a factor of a few hundreds for Plutonium and minor actinides recycling scenarios. This gain is nearly independent on the reactor type used, but needs about 100 years of application to become effective in terms of making a difference in the total waste inventory to be disposed of

New insights into thorium and uranium oxo-arsenic (III/V) and oxo-phosphates (V) crystal chemistry

International Nuclear Information System (INIS)

Yu, Na

2015-01-01

The fundamental chemistry of actinides is of great interest owing to the diverse number of valence states and complex coordination chemistry of the actinides. The phases based on actinides and oxo-salt fragments have been under thorough investigation in the last decades. These compounds can be widely found in nature and they affect the migration process of actinides in nature. A better understanding of the fundamental coordination chemistry of actinide compounds with oxo-salts of group V elements is not only important for understanding the actinides behavior within the migration process but can also be used to understand actinide properties in phosphate ceramics. Concerning the radioactive issues, the less radioactive early actinides (i.e. U, Th) can be taken as modeling elements to study the crystal chemistry of the transuranic elements (Np, Pu) without the major handling problems. This can be done as Th(IV) has a very similar coordination chemistry with An(IV) and U(VI) can be chosen as a modeling element for transuranic elements in higher valence states. Therefore, a systematic research on the actinides (U, Th) bearing phases with tetrahedral oxo-anions such as phosphates and arsenates have been performed in this work. High temperature (HT) solid state reaction, High pressure high temperature (HP-HT) solid state reaction and the hydrothermal method were the methods of choice for synthesizing actinide bearing oxo-arsenic(III/V) and oxo- phosphorus(V) phases in the past three years. As a result, numerous novel compounds containing actinides were obtained. The structures of all compounds were determined using single crystal X-ray diffraction data. Raman spectroscopy, EDS, DSC and high temperature powder X-ray diffraction (HT-PXRD) measurements were implemented to characterize the chemical and physical properties of the obtained compounds. The core of this dissertation is a fundamental study of the crystal chemistry of actinides (Th, U) oxo-arsenic (III/V) and oxo

Moessbauer effect studies with actinides

International Nuclear Information System (INIS)

Stone, J.A.

1966-01-01

Moessbauer resonance studies in the actinide elements offer a new technique for measuring solid-state properties to a region of the periodic chart where such information is relatively sparse. It is well known that the actinides, the elements with atomic numbers from 90 to 103, form a transition series due to filling of the 5f electron shell, analogous to the rare-earth series in which the 4f shell is filled. Like the rare earths, the actinide metals and compounds are expected to exhibit a variety of interesting magnetic properties, but, unlike the rare earths, there have been few studies of the magnetic behaviour of actinides, and these properties are largely unknown. The chemical properties of the actinides have been studied somewhat more extensively, and, in contrast to the rare earths, form a multiplicity of stable valence states, especially in the lighter members of the series. It is just these properties, magnetic and chemical, for which the Moessbauer effect is a valuable probe, sensitive to the magnetic and electric environment of an atom. The rare-earth series has been a particularly fruitful region in terms of the number of elements which have been shown to exhibit the Moessbauer effect, and for this reason the exploitation of the Moessbauer effect to yield new solid-state and chemical information on the rare earths is a highly active field of research today. There is every reason to believe that the actinides can be similarly studied by the Moessbauer effect. 43 refs, 6 figs, 4 tabs

Liquid-liquid extraction of U(VI), Np(V) et Th(IV) ions by two calix[4]arene carboxyls, and effect of Na+ and K+ alkaline ions

International Nuclear Information System (INIS)

Montavon, Gilles

1996-01-01

As the process mainly used for the reprocessing of nuclear wastes was the Purex process, this research thesis first presents this process and outlines that it allows the residual fissile matter to be recovered and reused for the fabrication of new fuel elements, but is neither efficient nor safe enough to separate fission and activation products. Thus, this thesis reports the study of extraction and selectivity properties of two compounds derived from the p-tert-butyl-calix[4]arene with respect to actinide ions such as Th(IV), U(VI) and Np(VI). The liquid-liquid extraction technique has been used with chloroform and 1,2-dichloroethane as solvents. After some generalities on actinides, calixarenes and the liquid-liquid extraction technique, and a presentation of the experimental method, the author reports and discusses the extractive properties of the studied calixarenes with respect to Na + and K + ions. Structural studies by proton NMR have been performed. He reports and discusses the liquid-liquid extraction on actinide ions when they are alone or in presence on Na + and K + alkaline ions [fr

Evaluation of actinide partitioning and transmutation

International Nuclear Information System (INIS)

1982-01-01

After a few centuries of radioactive decay the long-lived actinides, the elements of atomic numbers 89-103, may constitute the main potential radiological health hazard in nuclear wastes. This is because all but a very few fission products (principally technetium-99 and iodine-129) have by then undergone radioactive decay to insignificant levels, leaving the actinides as the principal radionuclides remaining. It was therefore at first sight an attractive concept to recycle the actinides to nuclear reactors, so as to eliminate them by nuclear fission. Thus, investigations of the feasibility and potential benefits and hazards of the concept of 'actinide partitioning and transmutation' were started in numerous countries in the mid-1970s. This final report summarizes the results and conclusions of technical studies performed in connection with a four-year IAEA Co-ordinated Research Programme, started in 1976, on the ''Environmental Evaluation and Hazard Assessment of the Separation of Actinides from Nuclear Wastes followed by either Transmutation or Separate Disposal''. Although many related studies are still continuing, e.g. on waste disposal, long-term safety assessments, and waste actinide management (particularly for low and intermediate-level wastes), some firm conclusions on the overall concept were drawn by the programme participants, which are reflected in this report

Structure and dynamics of hydrated Fe(II) and Fe(III) ions. Quantum mechanical and molecular mechanical simulations

International Nuclear Information System (INIS)

Remsungnen, T.

2002-11-01

Classical molecular dynamics (MD) and combined em ab initio quantum mechanical/molecular mechanical molecular dynamics (QM/MM-MD) simulations have been performed to investigate structural, dynamical and energetical properties of Fe(II), and Fe(III) transition metal ions in aqueous solution. In the QM/MM-MD simulations the ion and its first hydration sphere were treated at the Hartree-Fock ab initio quantum mechanical level, while ab initio generated pair plus three-body potentials were employed for the remaining system. For the classical MD simulation the pair plus three-body potential were employed for all ion-water interactions. The coordination number of the first hydration shell is 100 % of 6 in both cases. The number of waters in the second hydration shell obtained from classical simulations are 13.4 and 15.1 for Fe(II) and Fe(III), respectively, while QM/MM-MD gives the values of 12.4 and 13.4 for Fe(II) and Fe(III). The energies of hydration obtained from MD and QM/MM-MD for Fe(II) are 520 and 500 kcal/mol, and for Fe(III) 1160 and 1100 kcal/mol respectively. The mean residence times of water in the second shell obtained from QM/MM-MD are 24 and 48 ps for Fe(II) and Fe(III), respectively. In contrast to the data obtained from classical MD simulation, the QM/MM-MD values are all in good agreement with the experimental data available. These investigations and results clearly indicate that many-body effects are essential for the proper description of all properties of the aqueous solution of both Fe(II) and Fe(III) ions. (author)

Complexation studies of actinides (U, Pu, Am) with linear polyamino-carboxylate ligands and sidero-chelates

International Nuclear Information System (INIS)

Nguyen, L.V.

2010-01-01

As part of our research endeavour aimed at developing and improving decontamination processes of wastewater containing alpha emitters, physico-chemical complexation studies of actinides (U, Pu, Am) with organic open-chain ligands such as poly-aminocarboxylic acids (H 4 EDTA) and sidero-chelates (di-hydroxamic acids and desferrioxamine B) have been carried out. Gaining a clear understanding of the coordination properties of the targeted actinides is an essential step towards the selection of the most appropriate chelating agents that will exhibit high uptake efficiencies. EXAFS (Extended X-ray Absorption Fine Structure) measurements at the ESRF synchrotron enabled to elucidate the coordination scheme of uranium and plutonium complexes. Solution thermodynamic investigations were intended to provide valuable information about the nature and the stability of the uranium(VI) and americium(III) complexes prevailing at a given pH in solution. The set of stability constants determined from potentiometric and UV-visible spectrophotometric titrations, allowed to predict the speciation of the selected actinides in presence of the aforementioned ligands and to determine the pH range required for achieving 'ultimate' decontamination. (author) [fr

Intramolecular electron transfer through a bridging carboxylate group coordinated to two cobalt(III)-ions

International Nuclear Information System (INIS)

Wieghardt, K.

1978-01-01

Reduction of the binuclear μ-p-nitrobenzoato -di-μ-hydroxo -bis[triammine cobalt(III)] cation with (CH 3 ) 2 COH radicals yields a radical cation with the p-nitrobenzoato radical being coordinated to two cobalt(III) ions at the carboxylic group. The unprotonated form of this species undergoes intramolecular electron transfer producing Co(II) (k = (3.3 +- 0.3). x 10 3 s -1 ). The role of the carboxylate group in the intramolecular electron transfer process is tentatively assessed in terms of an intramolecular outer-sphere reaction because of lack of overlap of the donor orbitals (π) and the acceptor orbital (sigma). The protonated form of the radical cation (pKsub(a) = 2.5) disproportionates via a bimolecular process without production of Co(II). The effect of two coordinated Co(III) ions as compared to only one on the properties of the nitrobenzoate radical anion are discussed. (orig.) 891 HK 892 GM [de

Comparative studies of actinide and sub-actinide fission cross section calculation from MCNP6 and TALYS

International Nuclear Information System (INIS)

Perkasa, Y. S.; Waris, A.; Kurniadi, R.; Su'ud, Z.

2014-01-01

Comparative studies of actinide and sub-actinide fission cross section calculation from MCNP6 and TALYS have been conducted. In this work, fission cross section resulted from MCNP6 prediction will be compared with result from TALYS calculation. MCNP6 with its event generator CEM03.03 and LAQGSM03.03 have been validated and verified for several intermediate and heavy nuclides fission reaction data and also has a good agreement with experimental data for fission reaction that induced by photons, pions, and nucleons at energy from several ten of MeV to about 1 TeV. The calculation that induced within TALYS will be focused mainly to several hundred MeV for actinide and sub-actinide nuclides and will be compared with MCNP6 code and several experimental data from other evaluator

Influence of additives on the structure and microstructure of lanthanides and actinides oxalates

International Nuclear Information System (INIS)

Haidon, Blaise; Vitart, Anne-Lise; Rivenet, Murielle; Arab-Chapelet, Benedicte; Roussel, Pascal; Delahaye, Thibaud; Grandjean, Stephane; Abraham, Francis

2015-07-01

Oxalic conversion is a well-known process in the nuclear industry where it is used for precipitating plutonium as an oxalate thereafter calcinated into an oxide. As there is a strong relationship between the morphology of the oxalate precursor and that of the resulting oxide, it is of interest to control the oxalate structure and microstructure during the precipitation step. The influence of additives on the precipitation of neodymium (III) oxalates, non-radioactive analogs of actinides (III) oxalates, was explored. With the use of nitrilotri-methylphosphonic acid (NTMP), the structure and microstructure of the neodymium oxalates are different from that obtained without additive. (authors)

Lutetium(III) aqua ion: On the dynamical structure of the heaviest lanthanoid hydration complex

Energy Technology Data Exchange (ETDEWEB)

Sessa, Francesco; D’Angelo, Paola, E-mail: p.dangelo@uniroma1.it [Dipartimento di Chimica, Università di Roma “La Sapienza,” P. le A. Moro 5, 00185 Roma (Italy); Spezia, Riccardo [CNRS, UMR 8587, Laboratoire Analyse et Modelisation Pour la Biologie et l’Environnement, Université d’Evry Val d’Essonne, Blvd. F. Mitterrand, 91025 Evry Cedex (France)

2016-05-28

The structure and dynamics of the lutetium(III) ion in aqueous solution have been investigated by means of a polarizable force field molecular dynamics (MD). An 8-fold square antiprism (SAP) geometry has been found to be the dominant configuration of the lutetium(III) aqua ion. Nevertheless, a low percentage of 9-fold complexes arranged in a tricapped trigonal prism (TTP) geometry has been also detected. Dynamic properties have been explored by carrying out six independent MD simulations for each of four different temperatures: 277 K, 298 K, 423 K, 632 K. The mean residence time of water molecules in the first hydration shell at room temperature has been found to increase as compared to the central elements of the lanthanoid series in agreement with previous experimental findings. Water exchange kinetic rate constants at each temperature and activation parameters of the process have been determined from the MD simulations. The obtained structural and dynamical results suggest that the water exchange process for the lutetium(III) aqua ion proceeds with an associative mechanism, in which the SAP hydration complex undergoes temporary structural changes passing through a 9-fold TTP intermediate. Such results are consistent with the water exchange mechanism proposed for heavy lanthanoid atoms.

Supercritical Carbon Dioxide-Soluble Ligands for Extracting Actinide Metal Ions from Porous Solids

International Nuclear Information System (INIS)

Joan Brennecke; Mark Dietz; Richard Barrans; Alabert Herlinger

2003-01-01

Numerous types of actinide-bearing waste materials are found throughout the DOE complex. Most of these wastes consist of large volumes of non-hazardous materials contaminated with relatively small quantities of actinide elements. Separation of these wastes into their inert and radioactive components would dramatically reduce the costs of stabilization and disposal. For example, the DOE is responsible for decontaminating concrete within 7000 surplus contaminated buildings. The best technology now available for removing surface contamination from concrete involves removing the surface layer by grit blasting, which produces a large volume of blasting residue containing a small amount of radioactive material. Disposal of this residue is expensive because of its large volume and fine particulate nature. Considerable cost savings would result from separation of the radioactive constituents and stabilization of the concrete dust. Similarly, gas diffusion plants for uranium enrichment contain valuable high-purity nickel in the form of diffusion barriers. Decontamination is complicated by the extremely fine pores in these barriers, which are not readily accessible by most cleaning techniques. A cost-effect method for the removal of radioactive contaminants would release this valuable material for salvage

Preparation of minor actinides targets or blankets by the means of Ionic Exchange Resin

Energy Technology Data Exchange (ETDEWEB)

Picart, S.; Mokhtari, H.; Ramiere, I.; Jobelin, I. [CEA, Nuclear Energy Division, RadioChemistry and Process Department, Actinides Chemistry Laboratory, BP17171, Bagnols-sur-Ceze, 30207 (France)

2009-06-15

The objective of our R and D work is the elaboration by the use of ionic exchange resin of minor actinide precursors for target or blanket dedicated to their transmutation in sodium fast reactor. From the beginning, the resin process called WAR (acronym of Weak Acid Resin) was developed in the 70's at the ORNL for the making of uranium carbide kernels for the high temperature gas reactor [1] [2]. By now, our aim is to extend this concept to the manufacturing of minor actinides oxide mixed with uranium oxides [3]. More precisely, this process can be divided in two major steps: the loading of the resin and the thermal treatment of the fully loaded resin driving either to oxide or carbide phases depending on the gas atmosphere. The difficulty stems from the preparation of the loading solutions which must fulfill precise conditions of pH in presence of actinides cations prone to hydrolysis. Furthermore, the proportions of uranium and minor actinides in solutions must be adjusted to fit the right ratio in the solid. The study presented here will then focus on the experiments and tests which enable us to optimize the fixing of minor actinides on ionic exchange resin and their carbonization in oxide. [1] G. W. Weber, R. L. Beatty et V. J. Tennery, Nuclear Technology, 35, 217-226, (1977), 'Processing and composition control of weak-acid-resin derived fuel microspheres'. [2] K. J. Notz, P. A. Haas, J. H. Shaffer, Radiochimica Acta, 25, 153-160, (1978). 'The preparation of HTGR Fissile Fuel Kernels by Uranium Loading of Ion Exchange Resin'. [3] S. Picart, H. Mokhtari, I. Ramiere, 'Plutonium Futures, The Science 2008', 7-11 july 2008, Dijon, France. 'Modelling of the ionic Exchange between a weak acid resin in its ammonium form and a minor actinide'. (authors)

Actinide nanoparticle research

International Nuclear Information System (INIS)

Kalmykov, Stepan N.; Denecke, Melissa A.

2011-01-01

This is the first book to cover actinide nano research. It is of interest both for fundamental research into the chemistry and physics of f-block elements as well as for applied researchers such as those studying the long-term safety of nuclear waste disposal and developing remediation strategies. The authors cover important issues of the formation of actinide nano-particles, their properties and structure, environmental behavior of colloids and nanoparticles related to the safe disposal of nuclear wastes, modeling and advanced methods of characterization at the nano-scale. (orig.)

Spectroscopic investigations on the complexation of Cm(III) and Eu(III) with organic model ligands and their binding mode in human urine (in vitro)

International Nuclear Information System (INIS)

Heller, Anne

2011-01-01

In case of incorporation, trivalent actinides (An(III)) and lanthanides (Ln(III)) pose a serious health risk to humans. An(III) are artificial, highly radioactive elements which are mainly produced during the nuclear fuel cycle in nuclear power plants. Via hazardous accidents or nonprofessional storage of radioactive waste, they can be released in the environment and enter the human food chain. In contrast, Ln(III) are nonradioactive, naturally occurring elements with multiple applications in technique and medicine. Consequently it is possible that humans get in contact and incorporate both, An(III) and Ln(III). Therefore, it is of particular importance to elucidate the behaviour of these elements in the human body. While macroscopic processes such as distribution, accumulation and excretion are studied quite well, knowledge about the chemical binding form (speciation) of An(III) and Ln(III) in various body fluids is still sparse. In the present work, for the first time, the speciation of Cm(III) and Eu(III) in natural human urine (in vitro) has been investigated spectroscopically and the formed complex identified. For this purpose, also basic investigations on the complex formation of Cm(III) and Eu(III) in synthetic model urine as well as with the urinary relevant, organic model ligands urea, alanine, phenylalanine, threonine and citrate have been performed and the previously unknown complex stability constants determined. Finally, all experimental results were compared to literature data and predictions calculated by thermodynamic modelling. Since both, Cm(III) and Eu(III), exhibit unique luminescence properties, particularly the suitability of time-resolved laser-induced fluorescence spectroscopy (TRLFS) could be demonstrated as a method to investigate these metal ions in untreated, complex biofluids. The results of this work provide new scientific findings on the biochemical reactions of An(III) and Ln(III) in human body fluids on a molecular scale and

Burning minor actinides in a HTR energy spectrum

International Nuclear Information System (INIS)

Pohl, Christoph; Rütten, H. Jochem

2012-01-01

Highlights: ► Burn-up analysis for varying plutonium/minor actinide fuel compositions. ► The influence of varying heavy metal fuel element loads is investigated. ► Significant burn-up via radiative capture and subsequently fission is observed. ► Difference observed between fuel element burn-up and total actinide burning rate. - Abstract: The generation of nuclear energy by means of the existing nuclear reactor systems is based mainly on the fission of U-235. But this comes along with the capture of neutrons by the U-238 faction and results in a build-up of plutonium isotopes and minor actinides as neptunium, americium and curium. These actinides are dominant for the long time assessment of the radiological risk of a final disposal therefore a minimization of the long living isotopes is aspired. Burning the actinides in a high temperature helium cooled graphite moderated reactor (HTR) is one of these options. The use of plutonium isotopes to sustain the criticality of the system is intended to avoid on the one hand highly enriched uranium because of international regulations and on the other hand low enriched uranium because of the build up of new actinides from neutron capture in the U-238 fraction. Because initial minor actinide isotopes are typically not fissionable by thermal neutrons the idea is to fission instead the intermediate isotopes generated by the first neutron capture. This paper comprises calculations for plutonium/minor actinides/thorium fuel compositions and their correlated final burn-up for a generic pebble bed HTR based on the reference design of the 400 MW PBMR. In particular the cross sections and the neutron balance of the different minor actinide isotopes in the higher thermal energy spectrum of a HTR will be discussed. For a fuel mixture of plutonium and minor actinides a significant burn-up of these actinides up to 20% can be achieved but at the expense of a higher residual fraction of plutonium in the burned fuel. Combining

Actinides reduction by recycling in a thermal reactor

International Nuclear Information System (INIS)

Ramirez S, J. R.; Martinez C, E.; Balboa L, H.

2014-10-01

This work is directed towards the evaluation of an advanced nuclear fuel cycle in which radioactive actinides could be recycled to remove most of the radioactive material; firstly a production reference of actinides in standard nuclear fuel of uranium at the end of its burning in a BWR reactor is established, after a fuel containing plutonium is modeled to also calculate the actinides production in MOX fuel type. Also it proposes a design of fuel rod containing 6% of actinides in a matrix of uranium from the tails of enrichment, then four standard uranium fuel rods are replaced by actinides rods to evaluate the production and transmutation thereof, the same procedure was performed in the fuel type MOX and the end actinide reduction in the fuel was evaluated. (Author)

High frequency ion sound waves associated with Langmuir waves in type III radio burst source regions

Directory of Open Access Journals (Sweden)

G. Thejappa

2004-01-01

Full Text Available Short wavelength ion sound waves (2-4kHz are detected in association with the Langmuir waves (~15-30kHz in the source regions of several local type III radio bursts. They are most probably not due to any resonant wave-wave interactions such as the electrostatic decay instability because their wavelengths are much shorter than those of Langmuir waves. The Langmuir waves occur as coherent field structures with peak intensities exceeding the Langmuir collapse thresholds. Their scale sizes are of the order of the wavelength of an ion sound wave. These Langmuir wave field characteristics indicate that the observed short wavelength ion sound waves are most probably generated during the thermalization of the burnt-out cavitons left behind by the Langmuir collapse. Moreover, the peak intensities of the observed short wavelength ion sound waves are comparable to the expected intensities of those ion sound waves radiated by the burnt-out cavitons. However, the speeds of the electron beams derived from the frequency drift of type III radio bursts are too slow to satisfy the needed adiabatic ion approximation. Therefore, some non-linear process such as the induced scattering on thermal ions most probably pumps the beam excited Langmuir waves towards the lower wavenumbers, where the adiabatic ion approximation is justified.

PRODUCTION OF ACTINIDE METAL

Science.gov (United States)

Knighton, J.B.

1963-11-01

A process of reducing actinide oxide to the metal with magnesium-zinc alloy in a flux of 5 mole% of magnesium fluoride and 95 mole% of magnesium chloride plus lithium, sodium, potassium, calcium, strontium, or barium chloride is presented. The flux contains at least 14 mole% of magnesium cation at 600-- 900 deg C in air. The formed magnesium-zinc-actinide alloy is separated from the magnesium-oxide-containing flux. (AEC)

A Novel Sensor for Monitoring of Iron(III) Ions Based on Porphyrins

Science.gov (United States)

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A3B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10−7–1 × 10−1 M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples. PMID:22969395

Luminescent single-ion magnets from Lanthanoid(III) complexes with monodentate ketone ligands

Energy Technology Data Exchange (ETDEWEB)

Kanetomo, Takuya; Ishida, Takayuki, E-mail: takayuki.ishida@uec.ac.jp [Department of Engineering Science, The University of Electro-Communications, Tokyo (Japan)

2016-02-01

We synthesized [Ln{sup III}(hfac){sub 3}(H{sub 2}O)(L)] (abbreviated as Ln-L; Ln = Gd, Tb, Eu; L = DTBK (di-t-butyl ketone), BP (benzophenone)), in which the carbonyl oxygen atom was coordinated to the Ln ion center, despite of such bulky substituents. Their crystal structures were determined by means of X-ray diffraction study. Gd-DTBK is completely isomorphous to the di-t-butyl nitroxide derivative and accordingly can be regarded as a model with the ligand spin masked. The ac magnetic susceptibility measurements on Tb-DTBK and -BP showed frequency dependence, characteristic of single-ion magnets. They also displayed photoluminescence in the solid state at room temperature. The quantum yields of the luminescence of Tb-DTBK and -BP (λ{sub ex} = 360 nm) were improved to 57 and 35%, respectively, from that of the starting material [TbI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] (28% at λ{sub ex} = 370 nm). Similarly, the quantum yields for Eu-DTBK and -BP were 8 and 15%, respectively, with λ{sub ex} = 400 nm, while that of the starting material [EuI{sup III}(hfac){sub 3}(H{sub 2}O){sub 2}] was 4% at λ{sub ex}=400 nm.

A novel sensor for monitoring of iron(III) ions based on porphyrins.

Science.gov (United States)

Vlascici, Dana; Fagadar-Cosma, Eugenia; Popa, Iuliana; Chiriac, Vlad; Gil-Agusti, Mayte

2012-01-01

Three A(3)B porphyrins with mixed carboxy-, phenoxy-, pyridyl-, and dimethoxy-substituent functionalization on the meso-phenyl groups were obtained by multicomponent synthesis, fully characterized and used as ionophores for preparing PVC-based membrane sensors selective to iron(III). The membranes have an ionophore:PVC:plasticizer composition ratio of 1:33:66. Sodium tetraphenylborate was used as additive (20 mol% relative to ionophore). The performance characteristics (linear concentration range, slope and selectivity) of the sensors were investigated. The best results were obtained for the membrane based on 5-(4-carboxyphenyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin plasticized with bis(2-ethylhexyl)sebacate, in a linear range from 1 × 10(-7)-1 × 10(-1) M with a slope of 21.6 mV/decade. The electrode showed high selectivity with respect to alkaline and heavy metal ions and a response time of 20 s. The influence of pH on the sensor response was studied. The sensor was used for a period of six weeks and the utility has been tested for the quantitative determination of Fe(III) in recovered solutions from spent lithium ion batteries and for the quantitative determination of Fe(III) in tap water samples.

Structural Characterization of Am(III)- and Pu(III)-DOTA Complexes.

Science.gov (United States)

Audras, Matthieu; Berthon, Laurence; Berthon, Claude; Guillaumont, Dominique; Dumas, Thomas; Illy, Marie-Claire; Martin, Nicolas; Zilbermann, Israel; Moiseev, Yulia; Ben-Eliyahu, Yeshayahu; Bettelheim, Armand; Cammelli, Sebastiano; Hennig, Christoph; Moisy, Philippe

2017-10-16

The complexation of 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) ligand with two trivalent actinides (Am 3+ and Pu 3+ ) was investigated by UV-visible spectrophotometry, NMR spectroscopy, and extended X-ray absorption fine structure in conjunction with computational methods. The complexation process of these two cations is similar to what has been previously observed with lanthanides(III) of similar ionic radius. The complexation takes place in different steps and ends with the formation of a (1:1) complex [(An(III)DOTA)(H 2 O)] - , where the cation is bonded to the nitrogen atoms of the ring, the four carboxylate arms, and a water molecule to complete the coordination sphere. The formation of An(III)-DOTA complexes is faster than the Ln(III)-DOTA systems of equivalent ionic radius. Furthermore, it is found that An-N distances are slightly shorter than Ln-N distances. Theoretical calculations showed that the slightly higher affinity of DOTA toward Am over Nd is correlated with slightly enhanced ligand-to-metal charge donation arising from oxygen and nitrogen atoms.

Potential carcinogenic effects of actinides in the environment

International Nuclear Information System (INIS)

Harley, N.H.; Pasternack, B.S.

1979-01-01

Inhalation of alpha emitting actinides delivers a dose to critical cancer sites in the human body. These sites are the bronchial epithelium and cells near bone surfaces. Inhalation of the naturally occurring actinides uranium and thorium in resuspended soil in the air results in a continuous exposure for the global population of about 0.1 fCi/m 3 for each of these actinides. The highest dose is from the natural actinide 230 Th. Over 50 yr, the dose to bronchial epithelium is 0.05 mrad and to bone surfaces 0.4 mrad. In the case of accidental environmental contamination (e.g. near a nuclear fuel reprocessing plant) the man-made actinides plutonium, americium and curium could deliver about the same alpha dose to these sites if the soil is contaminated to the same level as the natural actinides (approximately 1 pCi/g). Two nuclear accidents have already produced contamination of about this level. Exposures in this case, however, are to small local populations compared with global exposure for the natural actinides. Significant enhancement of the natural radioactive actinide pollution by combustion of all types of fossil fuel is suspected but not enough data are available to estimate total population doses. (author)

Effects on auto-irradiation on the solubility of mineral phases enriched by actinides

International Nuclear Information System (INIS)

Prot, T.

1993-07-01

The scope of the present work is to investigate possible effects of self-irradiation damage induced by α-decay (α-recoil nucleus and α-particle) on the hydrated layer formed by aqueous corrosion of nuclear glass and on alteration phases of a granitic geological repository (calcium carbonate or iron oxides and oxihydroxide) which would be likely irradiated in the framework of high-level radioactive waste disposal, for sufficient concentration of actinides and age. Our experimental procedure relies on a bombardment with external beams of 1.5 to 1.8 MeV He ions and 200 KeV Pb ions, which respectively simulate the radiation effects of α-particles and of α-recoil nuclei. We have observed in a first step, direct irradiation effects (change of volume and refractive index, chemical modification) by means of optical microscopy, microtopographical analysis (surface profilometer) and R.B.S. and X.P.S. In a second step, corrosion tests were performed in static conditions to observe a possible indirect effect (increase of the hydratation rate, actinide release) on the later evolution as for example, a marked increase in solubility (calcium carbonate case)

End point control of an actinide precipitation reactor

International Nuclear Information System (INIS)

Muske, K.R.

1997-01-01

The actinide precipitation reactors in the nuclear materials processing facility at Los Alamos National Laboratory are used to remove actinides and other heavy metals from the effluent streams generated during the purification of plutonium. These effluent streams consist of hydrochloric acid solutions, ranging from one to five molar in concentration, in which actinides and other metals are dissolved. The actinides present are plutonium and americium. Typical actinide loadings range from one to five grams per liter. The most prevalent heavy metals are iron, chromium, and nickel that are due to stainless steel. Removal of these metals from solution is accomplished by hydroxide precipitation during the neutralization of the effluent. An end point control algorithm for the semi-batch actinide precipitation reactors at Los Alamos National Laboratory is described. The algorithm is based on an equilibrium solubility model of the chemical species in solution. This model is used to predict the amount of base hydroxide necessary to reach the end point of the actinide precipitation reaction. The model parameters are updated by on-line pH measurements

On the suitability of lanthanides as actinide analogs

International Nuclear Information System (INIS)

Raymond, Kenneth; Szigethy, Geza

2008-01-01

With the current level of actinide materials used in civilian power generation and the need for safe and efficient methods for the chemical separation of these species from their daughter products and for long-term storage requirements, a detailed understanding of actinide chemistry is of great importance. Due to the unique bonding properties of the f-elements, the lanthanides are commonly used as structural and chemical models for the actinides, but differences in the bonding between these 4f and 5f elements has become a question of immediate applicability to separations technology. This brief overview of actinide coordination chemistry in the Raymond group at UC Berkeley/LBNL examines the validity of using lanthanide analogs as structural models for the actinides, with particular attention paid to single crystal X-ray diffraction structures. Although lanthanides are commonly accepted as reasonable analogs for the actinides, these comparisons suggest the careful study of actinide materials independent of their lanthanide analogs to be of utmost importance to present and future efforts in nuclear industries. (authors)

Interface reactions of actinides on muscovite; Grenzflaechenreaktionen von Actiniden an Muskovit

Energy Technology Data Exchange (ETDEWEB)

Hellebrandt, Stefan

2017-11-06

adsorbed U was detected at the muscovite interface according to all methods applied, despite the larger concentration of the adsorbate. This difference in the sorption behavior can be explained by the different redox behavior of U and Pu. U will stay mainly in its predominant oxidation state VI, due to its higher stability compared to Pu, while Pu will be present as Pu(VI), but also in a greater extent in its reduced oxidation states. Due to this difference Pu is able to form nanoparticles, whereas this is not the case for U. The third part compares the sorption of trivalent actinides Am(III) and Cm(III) and their homolog Eu(III) on alumino-silicates muscovite (phyllosilicate) and orthoclase (framework silicate). Under acidic conditions all elements adsorb as outer-sphere complexes, while the relative amount of inner-sphere sorption increases with increasing pH. At higher pH a transition from adsorbed aquoions to adsorbed hydrolysis-species and eventually a ternary sorption complex is observed. While TRLFS itself is a strong tool to investigate the speciation of metals in solution or in contact with a mineral surface the complementary use of SXS techniques is able to improve these findings. The results of this work, achieved by using modern methods such as X-ray scattering techniques (CTR/RAXR) and TRLFS, have afforded new insights into the surface reactivity of a wide range of actinides (Th, U, Pu, Am, and Cm) in contact with muscovite and orthoclase. New influence factors could be identified in the influence of the background electrolyte on the sorption behavior, where both cation and anion affect the actinide's retention. The different redox behavior of redox-active actinides like U and Pu also influenced the sorption behavior tremendously, even in contact with the redox-inactive mineral muscovite. The complementary use of surface X-ray diffraction and laser spectroscopic methods was instrumental to enable us to investigate the distribution, occupancy, and

Review of actinide decorporation with chelating agents

Energy Technology Data Exchange (ETDEWEB)

Ansoborlo, E. [CEA Valrho, Dir. de l' Energie Nucleaire (DEN/DRCP/CETAMA), 30 - Marcoule (France); Amekraz, B.; Moulin, Ch. [CEA Saclay, Dept. de Physico-Chimie (DEN/DPC/SECR), 91 - Gif sur Yvette (France); Moulin, V. [CEA Saclay, Dir. du Developpement et de l' Innovation Nucleares (DEN/DDIN/MR), 91 - Gif Sur Yvette (France); Taran, F. [CEA Saclay (DSV/DBJC/SMMCB), 91 - Gif-sur-Yvette (France); Bailly, Th.; Burgada, R. [Centre National de la Recherche Scientifique (CNRS/LCSB/UMR 7033), 93 - Bobigny (France); Henge-Napoli, M.H. [CEA Valrho, Site de Marcoule (INSTN), 30 (France); Jeanson, A.; Den Auwer, Ch.; Bonin, L.; Moisy, Ph. [CEA Valrho, Dir. de l' Energie Nucleaire (DEN/DRCP/SCPS), 30 - Marcoule (France)

2007-10-15

In case of accidental release of radionuclides in a nuclear facility or in the environment, internal contamination (inhalation, ingestion or wound) with actinides represents a severe health risk to human beings. It is therefore important to provide effective chelation therapy or decorporation to reduce acute radiation damage, chemical toxicity, and late radiation effects. Speciation governs bioavailability and toxicity of elements and it is a prerequisite tool for the design and success of new ligands or chelating agents. The purpose of this review is to present the state-of-the-art of actinide decorporation within biological media, to recall briefly actinide metabolism, to list the basic constraints of actinide-ligand for development, to describe main tools developed and used for decorporation studies, to review mainly the chelating agents tested for actinides, and finally to conclude on the future trends in this field. (authors)

Transmutation of waste actinides in light water reactors

International Nuclear Information System (INIS)

Gorrell, T.C.

1979-04-01

Actinide recycle and transmutation calculations were made for three irradiation options of a light water reactor (LWR). The cases considered were: all actinides recycled in regular uranium fuel assemblies; transuranic actinides recycled in separate MOX assemblies with 235 U enrichment of uranium; and transuranic actinides recycled in separate MOX assemblies with plutonium enrichment of natural uranium. When all actinides were recycled in a uniform lattice, the transuranic inventory after ten recycles was 38% of the inventory accumulated without recycle. When the transuranics from two regular uranium assemblies were combined with those recycled from a MOX assembly, the transuranic inventory was reduced 50% after five recycles

Chemical compatibility of HLW borosilicate glasses with actinides

International Nuclear Information System (INIS)

Walker, C.T.; Scheffler, K.; Riege, U.

1978-11-01

During liquid storage of HLLW the formation of actinide enriched sludges is being expected. Also during melting of HLW glasses an increase of top-to-bottom actinide concentrations can take place. Both effects have been studied. Besides, the vitrification of plutonium enriched wastes from Pu fuel element fabrication plants has been investigated with respect to an isolated vitrification process or a combined one with the HLLW. It is shown that the solidification of actinides from HLLW and actinide waste concentrates will set no principal problems. The leaching of actinides has been measured in salt brine at 23 0 C and 115 0 C. (orig.) [de

A colorimetric and luminescent dual-modal assay for Cu(II ion detection using an iridium(III complex.

Directory of Open Access Journals (Sweden)

Dik-Lung Ma

Full Text Available A novel iridium(III complex-based chemosensor bearing the 5,6-bis(salicylideneimino-1,10-phenanthroline ligand receptor was developed, which exhibited a highly sensitive and selective color change from colorless to yellow and a visible turn-off luminescence response upon the addition of Cu(II ions. The interactions of this iridium(III complex with Cu2+ ions and thirteen other cations have been investigated by UV-Vis absorption titration, emission titration, and 1H NMR titration.

Interaction of trivalent lanthanides and actinides with aluminium oxides and hydroxides; Wechselwirkung von dreiwertigen Lanthaniden und Actiniden mit Aluminiumoxiden und -hydroxiden

Energy Technology Data Exchange (ETDEWEB)

Kupcik, Tomas

2011-10-28

The subject of the present work is the interaction of trivalent actinides Cm(III) and lanthanides (Eu(III) and Gd(III)) with aluminium oxides and -hydroxides, namely corundum/sapphire (α-Al{sub 2}O{sub 3}), gibbsite (α-Al(OH){sub 3}) and bayerite (β-Al(OH){sub 3}), as well as the polyoxocations ''Al{sub 13}'' (Al{sub 13}O{sub 4}(OH){sub 24}(H{sub 2}O){sub 12}{sup 7+}) and ''GaAl{sub 12}'' (GaO{sub 4}Al{sub 12}(OH){sub 24}(H{sub 2}O){sub 12}{sup 7+}). These investigations should contribute to a sound understanding of the solution-mineral-interface reactions relevant for the migration of radionuclides (in particular the actinides) in the near and far field of a repository for high-level radioactive waste in deep geological formations, e.g. adsorption and structural incorporation. Batch sorption studies show similar logK{sub d} values for Eu(III) sorption onto corundum and bayerite at low metal ion concentrations ([M(III)] ∝ 7.10{sup -7} M). These similarities can be related to the formation of Al-OH groups on the aluminium oxide surfaces. Comparable logK{sub d} values could be found in earlier investigations for Gd(III) sorbed onto γ-Al{sub 2}O{sub 3}. In agreement with the batch sorption results at trace metal ion concentrations, time resolved laser fluorescence spectroscopy (TRLFS) studies on the interaction of Cm(III) with corundum and bayerite suggest a similar Cm(III) speciation between pH = 3 and 13. Three different surface sorbed Cm(III) species can be distinguished for these mineral phases ([surface..Cm(OH){sub x}(H{sub 2}O){sub 5-x}]{sup 3-x} with x = 0, 1, 2). Comparable TRLFS results can also be found for Cm(III) sorbed on the sapphire (001) single crystal surface and on ''Al{sub 13}'' and ''GaAl{sub 12}''. In the Cm(III)/gibbsite system, spectroscopic results show clear differences in comparison to bayerite, corundum and γ-Al{sub 2}O{sub 3}, e.g. a Cm(III) species of

Effect of operating parameters on indium (III) ion removal by iron electrocoagulation and evaluation of specific energy consumption

Energy Technology Data Exchange (ETDEWEB)

Chou, Wei-Lung, E-mail: wlchou0388@hotmail.com [Department of Safety, Health and Environmental Engineering, Hungkuang University, Sha-Lu, Taichung 433, Taiwan (China); Wang, Chih-Ta [Department of Safety Health and Environmental Engineering, Chung Hwa University of Medical Technology, Tainan Hsien 717, Taiwan (China); Huang, Kai-Yu [Department of Safety, Health and Environmental Engineering, Hungkuang University, Sha-Lu, Taichung 433, Taiwan (China)

2009-08-15

The aim of this study is to investigate the effects of operating parameters on the specific energy consumption and removal efficiency of synthetic wastewater containing indium (III) ions by electrocoagulation in batch mode using an iron electrode. Several parameters, including different electrode pairs, supporting electrolytes, initial concentration, pH variation, and applied voltage, were investigated. In addition, the effects of applied voltage, supporting electrolyte, and initial concentration on indium (III) ion removal efficiency and specific energy consumption were investigated under the optimum balance of reasonable removal efficiency and relative low energy consumption. Experiment results indicate that a Fe/Al electrode pair is the most efficient choice of the four electrode pairs in terms of energy consumption. The optimum supporting electrolyte concentration, initial concentration, and applied voltage were found to be 100 mg/l NaCl, 20 mg/l, and 20 V, respectively. A higher pH at higher applied voltage (20 or 30 V) enhanced the precipitation of indium (III) ion as insoluble indium hydroxide, which improved the removal efficiency. Results from the indium (III) ion removal kinetics show that the kinetics data fit the pseudo second-order kinetic model well. Finally, the composition of the sludge produced was characterized with energy dispersion spectra (EDS).

Effect of operating parameters on indium (III) ion removal by iron electrocoagulation and evaluation of specific energy consumption

International Nuclear Information System (INIS)

Chou, Wei-Lung; Wang, Chih-Ta; Huang, Kai-Yu

2009-01-01

The aim of this study is to investigate the effects of operating parameters on the specific energy consumption and removal efficiency of synthetic wastewater containing indium (III) ions by electrocoagulation in batch mode using an iron electrode. Several parameters, including different electrode pairs, supporting electrolytes, initial concentration, pH variation, and applied voltage, were investigated. In addition, the effects of applied voltage, supporting electrolyte, and initial concentration on indium (III) ion removal efficiency and specific energy consumption were investigated under the optimum balance of reasonable removal efficiency and relative low energy consumption. Experiment results indicate that a Fe/Al electrode pair is the most efficient choice of the four electrode pairs in terms of energy consumption. The optimum supporting electrolyte concentration, initial concentration, and applied voltage were found to be 100 mg/l NaCl, 20 mg/l, and 20 V, respectively. A higher pH at higher applied voltage (20 or 30 V) enhanced the precipitation of indium (III) ion as insoluble indium hydroxide, which improved the removal efficiency. Results from the indium (III) ion removal kinetics show that the kinetics data fit the pseudo second-order kinetic model well. Finally, the composition of the sludge produced was characterized with energy dispersion spectra (EDS).

Study of the oxidation-reduction kinetics involved in the Np(V) + Fe(II) in equilibrium Np(IV) + Fe(III) system in nitric acid solutions

International Nuclear Information System (INIS)

Jao, Y.

1975-08-01

Ferrous nitrate-hydrazine is one of the more attractive alternate reactants to the currently used reagent, ferrous sulfamate, for partitioning plutonium from neptunium and uranium. An understanding of the kinetics of the reduction of Np(VI) to Np(IV) by ferrous nitrate-hydrazine is needed before a satisfactory evaluation of the feasibility of this reductant in actinide element separations can be made. The purpose of this work was to study the kinetics and mechanisms of the reduction of Np(V) by Fe(II) and the oxidation of Np(IV) by Fe(III) in 1-2 M nitric acid solutions. The acid concentration range was chosen to include that typically used in the separation of plutonium from neptunium and uranium by solvent extraction with tributylphosphate. The forward and reverse rate constants, hydrogen ion dependence, temperature dependence, ionic strength effects and nitrate ion influence were determined. The proposed reaction mechanisms involve protonation of the NpO 2 + ions and hydroxyoxygenation of Np 4 + ions. (LK)

Spectroscopic studies on the interaction of europium(III) and curium(III) with components of the human mucosa

Energy Technology Data Exchange (ETDEWEB)

Wilke, Claudia; Barkleit, Astrid [Helmholtz-Zentrum Dresden-Rossendorf e.V., Dresden (Germany). Div. Chemistry of the F-Elements

2016-07-01

To evaluate the health risks of lanthanides (Ln) and radiotoxic actinides (An) in case of ingestion accidents etc., investigations into the chemical reactions of these metals in the human gastrointestinal tract are necessary. Our previous study revealed that mucin, an important part of the protective mucosa layer in the digestive system, shows a strong interaction with Eu(III). Based on these results, the present study focuses on the components of this glycoprotein and identified N-acetylneuraminic acid (NANA) as the dominant binding carbohydrate of mucin. TRLFS measurements suggest the formation of a 1: 1 complex with log β of 3.2 ± 0.1 for Eu(III) and 3.3 ± 0.1 for Cm(III), respectively.

Advances in computational actinide chemistry in China

Energy Technology Data Exchange (ETDEWEB)

Wang, Dongqi; Wu, Jingyi; Chai, Zhifang [Chinese Academy of Sciences, Beijing (China). Multidisciplinary Initiative Center; Su, Jing [Chinese Academy of Sciences, Shanghai (China). Div. of Nuclear Materials Science and Engineering; Li, Jun [Tsinghua Univ., Beijing (China). Dept. of Chemistry and Laboratory of Organic Optoelectronics and Molecular Engineering

2014-04-01

The advances in computational actinide chemistry made in China are reviewed. Several areas relevant to chemistry of actinides in gas, liquid, and solid phases have been explored. However, we limit the scope to selected contributions in the chemistry of molecular actinide systems in gas and liquid phases. These studies may be classified into two categories: treatment of relativistic effects, which cover the development of two- and four-component Hamiltonians and the optimization of relativistic pseudopotentials, and the applications of theoretical methods in actinide chemistry. The applications include (1) the electronic structures of actinocene, noble gas complexes, An-C multiple bonding compounds, uranyl and its isoelectronic species, fluorides and oxides, molecular systems with metal-metal bonding in their isolated forms (U{sub 2}, Pu{sub 2}) and in fullerene (U{sub 2} rate at C{sub 60}), and the excited states of actinide complexes; (2) chemical reactions, including oxidation, hydrolysis of UF{sub 6}, ligand exchange, reactivities of thorium oxo and sulfido metallocenes, CO{sub 2}/CS{sub 2} functionalization promoted by trivalent uranium complex; and (3) migration of actinides in the environment. A future outlook is discussed. (orig.)

Solubilities of Actinide Oxides in the KURT Groundwater

International Nuclear Information System (INIS)

Kim, Seung Soo; Baik, Min Hoon; Choi, Jong Won

2009-12-01

For the estimation of solubilities of actinides in a deep underground condition, The solubilities of UO 2 , ThO 2 , NpO 2 and Am(OH) 3 in the KURT ground water have been measured under various redox conditions, and their solubilities and aqueous species in the same conditions as the experimental solutions were also calculated by using a geochemical code. Then these results were compared with each other as well as with literature results. For the calculation of solubility of a radionuclide, the thermodynamic data of the radionuclide complex from OECD/NEA, Nagra/PSI, KAERI, JAEA, SKB and recent literatures were collected and compared. Additionally, the methods for the correction of ionic strength and temperature of the solution were described in this report. The analysis techniques and recent research for measurement of species of actinides were also introduced. The concentrations of U, Th and Np dissolved were less than 10 -7 mol/L under Eh≤-0.2 of reducing condition from experiment and calculation, and the solubility of PuO 2 (cr) was estimated as lower than that of UO 2 (cr) by 1 ∼ 2 orders. However if amount of carbonate ion in the ground water increased, the concentration of tetra-valance actinides at pH 8 ∼ 11 would be greatly increased. The 1x10 -6 mol/L of americium might be a little conservative value in KURT groundwater. While carbonate or hydroxo-carbonatec complexes were presumed to be the dominant aqueous species in -0.2 ∼ -0.3 V of Eh and weakly alkaline solution, hydroxo complexes are dominant in strong reducing and high pH solution

Transmutation of minor actinide using thorium fueled BWR core

International Nuclear Information System (INIS)

Susilo, Jati