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Formation of plutonium(IV) colloid by the alpha-reduction of aqueous solutions of Pu(V) and Pu(VI)

Description: We describe concentration changes caused by chemical and alpha-induced radiolytic reactions in various oxidation state pure solutions of Pu(VI), Pu(V), or Pu(IV) colloid or mixtures of these oxidation states at pH values > 1 for a period of nearly two years. The rates of approach to steady-states and the resulting experimental concentration quotient values were determined in order to find the conditions under which equilibrium in 2PuO{sub 2}{sup +} + PuO{sub 2}{sup 2+} + PuO/sub 2(coll)/ reaction might be attained and to learn about the underlying reactions. Computer calculations were used to compare the data with the results required from proposed reaction schemes.
Date: December 31, 1985
Creator: Hobart, D.E.; Newton, T.W. & Palmer, P.D.
Partner: UNT Libraries Government Documents Department

{sup 13}C and {sup 17}O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

Description: Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} and (UO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = {minus}log(a{sub H}{sup +}) versus p[H] = {minus}log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA.
Date: January 1, 1995
Creator: Clark, D.L.; Newton, T.W.; Palmer, P.D. & Zwick, B.D.
Partner: UNT Libraries Government Documents Department

Plutonium carbonate speciation changes as measured in dilute solutions with photoacoustic spectroscopy: Yucca Mountain Site Characterization Program Milestone report 3350

Description: The stability fields for dilute Pu-carbonate species versus pH (8.4 to 12.0) and total carbonate concentrations (3 mM to 1.0 M) have been mapped-out using photoacoustic absorption spectroscopy (PAS). At least four different plutonium species, characterized by absorption peaks at 486, 492, 500, and 513 rim, have been found. A redox change to a Pu(VI) complex can not account for the speciation change associated with the first two spectra (486 and 492 nm peaks). Moreover, the data are consistent with what is predicted from a previous YMP milestone. This previous study was performed under very different conditions of plutonium concentration and carbonate/pH changes, and extension of these conditions to much lower Pu concentrations and to more neutral pHs was made possible with PAS spectroscopy. These new results reinforce the previous results by extending the range of direct observation and by eliminating other possibilities such as dimerization/polymerization reactions. As bicarbonate concentration is increased from .01 M to 1.0 M at pH=8.4 to 8.9, predominately [Pu(OH){sub x+1}(CO{sub 3}){sub y}]{sup 4-(x+2y)} (492 nm peak) is converted to [Pu(OH){sub x}(CO{sub 3}){sub y+l}]{sup 4-(x+2y+2)} (486 nm peak). The starting stoichiometry (x and y values) remain undetermined, but the effect of ionic strength and temperature indicate that the 486 nm species is highly charged, and therefore x+2y{ge}3. The temperature effect on the equilibrium between these two species was also investigated, with the species giving rise to the 486 nm peak reversibly losing importance at elevated (50 and 75{degrees}C temperatures).
Date: May 1, 1995
Creator: Tait, C.D.; Ekberg, S.A.; Palmer, P.D. & Morris, D.E.
Partner: UNT Libraries Government Documents Department

Formation, characterization, and stability of plutonium (IV) colloid; A progress report

Description: Plutonium is expected to be a major component of the waste element package in any high-level nuclear waste repository. Plutonium(IV) is known to form colloids under chemical conditions similar to those found in typical groundwaters. In the event of a breach of a repository, these colloids represent a source of radionuclide transport to the far-field environment, in parallel with the transport of dissolved waste element species. In addition, the colloids may decompose or disaggregate into soluble ionic species. Thus, colloids represent an additional term in determining waste element solubility limits. A thorough characterization of the physical and chemical properties of these colloids under relevant conditions is essential to assess the concentration limits and transport mechanisms for the waste elements at the proposed Yucca Mountain Repository site. This report is concerned primarily with recent results obtained by the Yucca Mountain Project (YMP) Solubility Determination Task pertaining to the characterization of the structural and chemical properties of Pu(IV) colloid. Important results will be presented which provides further evidence that colloidal plutonium(IV) is structurally similar to plutonium dioxide and that colloidal plutonium(IV) is electrochemically reactive. 13 refs., 7 figs.
Date: August 1989
Creator: Hobart, D. E.; Morris, D. E.; Palmer, P. D. & Newton, T. W.
Partner: UNT Libraries Government Documents Department

Report on neptunium speciation by NMR and optical spectroscopies

Description: Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.
Date: November 1, 1995
Creator: Tait, C.D.; Palmer, P.D.; Ekberg, S.A. & Clark, D.L.
Partner: UNT Libraries Government Documents Department

Actinide(IV) and actinide(VI) carbonate speciation studies by PAS and NMR spectroscopies; Yucca Mountain Project: Milestone report 3031-WBS

Description: Pulsed-laser photoacoustic spectroscopy (PAS) and Fourier-transform nuclear magnetic resonance (NMR) spectroscopy were used to study speciation of actinide(IV) and actinide(VI) ions (Np, Pu, Am) in aqueous carbonate solutions vs pH, carbonate content, actinide content, temperature. PAS focused on Pu(IV) speciation. Stability fields on a pH (8.4 to 12.0) versus total carbonate content (0.003 to 1.0 M) plot for dilute Pu(IV) carbonate species ([Pu]{sub tot} = 1 mM) were mapped. Four plutonium species, with absorption peaks at 486, 492, 500, and 512 nm were found. Loss of a single carbonate ligand does not account for the difference in speciation for the 486 and 492 nm absorption peaks, nor can any of the observed species be identified as colloidal Pu(IV). NMR data have been obtained for UO{sub 2}{sup 2+}, PuO{sub 2}{sup 2+} and AmO{sub 2}{sup 2+}. This report focuses on results for PuO{sub 2}{sup 2+}. The ligand exchange reaction between free and coordinated carbonate on the PuO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} systems has been examined by variable temperature {sup 13}C NMR spectroscopy. In each of the six different PuO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} samples, two NMR signals are present, one for the free carbonate ligand and one for the carbonate ligand coordinated to a paramagnetic plutonium metal center. The single{sup 13}C resonance line for coordinated carbonate is consistent with expectations of a monomeric PuO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} species in solution. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was used for determining ligand exchange parameters for paramagnetic actinide complexes. Eyring analysis at standard conditions provided activation parameters of {Delta}H = 38 KJ/M and {Delta}S = {minus}60 J/K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl(VI) carbonate complex self-exchange reaction.
Date: September 1, 1994
Creator: Clark, D.L.; Ekberg, S.A.; Morris, D.E.; Palmer, P.D. & Tait, C.D.
Partner: UNT Libraries Government Documents Department

Size determinations of plutonium colloids using autocorrelation photon spectroscopy

Description: Autocorrelation Photon Spectroscopy (APS) is a light-scattering technique utilized to determine the size distribution of colloidal suspensions. The capabilities of the APS methodology have been assessed by analyzing colloids of known sizes. Plutonium(IV) colloid samples were prepared by a variety of methods including: dilution; peptization; and alpha-induced auto-oxidation of Pu(III). The size of theses Pu colloids was analyzed using APS. The sizes determined for the Pu colloids studied varied from 1 to 370 nanometers. 7 refs., 5 figs., 3 tabs.
Date: December 1, 1989
Creator: Triay, I.R.; Rundberg, R.S.; Mitchell, A.J.; Ott, M.A.; Hobart, D.E.; Palmer, P.D. et al.
Partner: UNT Libraries Government Documents Department

Preparation of radioactive rare earth targets for neutron capture study

Description: The understanding of thc details of nucleosynthesis in stars remains a great challenge. Though the basic mechanisms governing the processes have been known since the pioneering work of Burbidge, Burbidge, Fowler and Hoyle (l), we are now evolving into a condition where we can ask more specific questions. Of particular interest are the dynamics of the s ('slow') process. In this process the general condition is one in which sequential neutron captures occur at time scales long compared with the beta decay half lives of the capturing nuclides. The nucleosynthesis period for C or Ne burning stellar shells is believed to be in the year to few year time frame (2). This means that radionuclides with similar half lives to this burning period serve as 'branch point' nuclides. That is, there will be a competition between a capture to the next heavier isotope and a beta decay to the element of nexl higher atomic number. By understanding the abundances of these competing reactions we can learn about the dynamics of the nucleosynthesis process in the stellar medium. Crucial to this understanding is that we have a knowledge of the underlying neutron reaction cross sections on these unstable nuclides in the relevant stellar energy regions (neutrons of 0.1-100 KeV). Tm (1.9 years) and ls'Sm (90 ycws) have decay properties that permit their handling in an open fume hood. These Iwo were therefore selected to be the first radionuclides for neutron capture study in what will be an ongoing effort.
Date: January 1, 2002
Creator: Miller, G. G. (Geoffrey G.); Rogers, P. S. Z. (Pamela S. Z.); Palmer, P. D. (Phillip D.); Dry, D. E. (Donald E.); Rundberg, R. S. (Robert S.); Fowler, Malcolm M. et al.
Partner: UNT Libraries Government Documents Department

Sorption of americium in tuff and pure minerals using synthetic and natural groundwaters

Description: The distribution of Am between selected solid and liquid phases has been studied using initial {sup 241}Am solutions with a molarity smaller than 1 {times} 10{sup {minus}11}. The synthetic and natural groundwaters used have pH values in the 7--8 range and a total alkalinity of approximately 1 mN which is mainly due to bicarbonate. Mass spectrometric isotope dilution was utilized to determine the amount of Am in the solution phase initially and after equilibrium was attained. Using this sensitive technique, 7 {times} 10{sup 8} atoms of {sup 241}Am were accurately measured. Our results indicate that the percent of Am lost to the walls of the container in the absence of geologic material varies from 35 to 84. The Am sorption coefficient determined is on the order of 10{sup 3} ml/g for clinoptilolite, 10{sup 4} ml/g for tuff consisting mainly of alkali feldspar and cristobalite, and 10{sup 5} ml/g for romanechite. 12 refs.
Date: December 1, 1989
Creator: Triay, I.R.; Meijer, A.; Cisneros, M.R.; Miller, G.G.; Mitchell, A.J.; Ott, M.A. et al.
Partner: UNT Libraries Government Documents Department

Carbon-13 NMR characterization of actinyl(VI) carbonate complexes in aqueous solution

Description: The uranyl(VI) carbonate system has been re-examined using {sup 13}C NMR of 99.9% {sup 13}C-enriched U{sup VI}O{sub 2} ({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} in millimolar concentrations. By careful control of carbonate ion concentration, we have confirmed the existence of the trimer, and observed dynamic equilibrium between the monomer and the timer. In addition, the ligand exchange reaction between free and coordinated carbonate on Pu{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} and Am{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} systems has been examined by variable temperature {sup 13}C NMR line-broadening techniques {sup 13}C NMR line-broadening techniques. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was written to allow for experimental determination of ligand exchange parameters for paramagnetic actinide complexes. Preliminary Eyring analysis has provided activation parameters of {Delta}G{sup {double dagger}}{sub 295} = 56 kJ/M, {Delta}H{sup {double dagger}} = 38 kJ/M, and {Delta}S{sup {double dagger}} = {minus}60 J/M-K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl (VI) carbonate complex self-exchange reaction. Experiments for determination of the activation parameters for the americium (VI) carbonate system are in progress.
Date: January 1, 1992
Creator: Clark, D.L.; Hobart, D.E.; Palmer, P.D. (Los Alamos National Lab., NM (United States)); Sullivan, J.C. (Argonne National Lab., IL (United States)) & Stout, B.E. (Cincinnati Univ., OH (United States). Dept. of Chemistry)
Partner: UNT Libraries Government Documents Department

DANCE : Device for Measurement of (n.g.) Reactions on radioactive Species /

Description: DANCE (Device for Advanced Neutron Capture Experiments) is a 4{pi} 162 element BaF{sub 2} array under development at Los Alamos National Laboratory. It is designed to provide high granularity, fast timing and high photon detection efficiency. It will be located at the Los Alamos Neutron Scattering Center where neutrons are produced using 800 MeV proton induced spallation reactions on heavy element production targets. Using the pulsed high neutron fluence available at this facility combined with time of flight techniques it will be possible to make neutron capture measurements in the neutron energy range from eV to 100's of keV on rare and radioactive target material at the milligram and below level. These measurements will provide critically needed data for the interpretation of the astrophysical s-process 'branching point' nuclei as well as information for reactions needed in understanding transmutation processes of radioactive species.
Date: January 1, 2001
Creator: Chamberlin, E. P. (Edwin P.); Dragowsky, M. (Michael); Fowler, Malcolm M.; Miller, G. G. (Geoffrey G.); Palmer, P. D. (Phillip D.); Pangualt, L. N. (Laurence N.) et al.
Partner: UNT Libraries Government Documents Department