Actinide Speciation in Spent Fuel Leaching Studies

1989 ◽  
Vol 176 ◽  
Author(s):  
Gregory R. Choppin
Keyword(s):  
Thermodynamic Data ◽  
Natural Waters ◽  
Spent Fuel ◽  
Model Calculations ◽  
Hydroxo Complexes ◽  
Uranyl Carbonate ◽  
Carbonate Complexes

ABSTRACTThe uranium and plutonium chemistry relevant for spent fuel leach studies is discussed. Model calculations are evaluated by comparison with the results of spent UO2 fuel leaching obtained in the Swedish SKB program. The thermodynamic data were found to agree sufficiently with the measured solution concentrations that it can be assumed that in oxic natural waters, leachate uranium from spent fuel would be uranyl carbonate complexes in the solution (or hydroxo complexes in the absence of carbonate) while schoepite would be the solubility limiting solid. For plutonium, PuO2+ would be the solution species and Pu(OH)4 the solubility limiting solid.

scholarly journals Uranium Speciation and Bioavailability in Aquatic Systems: An Overview

2002 ◽  
Vol 2 ◽  
pp. 707-729 ◽  
Author(s):  
Scott J. Markich
Keyword(s):  
Surface Waters ◽  
Metal Ion ◽  
Natural Waters ◽  
Analytical Techniques ◽  
Time Resolved ◽  
Analytical Technique ◽  
Major Form ◽  
Uranyl Carbonate ◽  
Inorganic Ligands ◽  
The Relationship

The speciation of uranium (U) in relation to its bioavailability is reviewed for surface waters (fresh- and seawater) and their sediments. A summary of available analytical and modeling techniques for determining U speciation is also presented. U(VI) is the major form of U in oxic surface waters, while U(IV) is the major form in anoxic waters. The bioavailability of U (i.e., its ability to bind to or traverse the cell surface of an organism) is dependent on its speciation, or physicochemical form. U occurs in surface waters in a variety of physicochemical forms, including the free metal ion (U4+or UO22+) and complexes with inorganic ligands (e.g., uranyl carbonate or uranyl phosphate), and humic substances (HS) (e.g., uranyl fulvate) in dissolved, colloidal, and/or particulate forms. Although the relationship between U speciation and bioavailability is complex, there is reasonable evidence to indicate that UO22+and UO2OH+are the major forms of U(VI) available to organisms, rather than U in strong complexes (e.g., uranyl fulvate) or adsorbed to colloidal and/or particulate matter. U(VI) complexes with inorganic ligands (e.g., carbonate or phosphate) and HS apparently reduce the bioavailability of U by reducing the activity of UO22+and UO2OH+. The majority of studies have used the results from thermodynamic speciation modeling to support these conclusions. Time-resolved laser-induced fluorescence spectroscopy is the only analytical technique able to directly determine specific U species, but is limited in use to freshwaters of low pH and ionic strength. Nearly all of the available information relating the speciation of U to its bioavailability has been derived using simple, chemically defined experimental freshwaters, rather than natural waters. No data are available for estuarine or seawater. Furthermore, there are no available data on the relationship between U speciation and bioavailability in sediments. An understanding of this relationship has been hindered due to the lack of direct quantitative U speciation techniques for particulate phases. More robust analytical techniques for determining the speciation of U in natural surface waters are needed before the relationship between U speciation and bioavailability can be clarified.

Metals speciation in Arctic lake under pollution impact (1980-2019): in-situ measurements, experimental estimates, model calculations

2020 ◽  
Author(s):  
Marina Dinu
Keyword(s):  
Membrane Filtration ◽  
Natural Waters ◽  
Metal Speciation ◽  
Wide Spectrum ◽  
Material Balance ◽  
Acidity Constant ◽  
Model Calculations ◽  
Membrane Pore ◽  
Arctic Lake ◽  
The Impact

<p>An important fundamental block in the geochemical studies is the evaluation of the equilibrium distribution of metals in water and the influence of environmental conditions on the spetiation. It is important to understand the difference between the behavior of nanoparticles, dissolved particles, colloid particles, and suspended particles. The research deals with study and assess of geochemical processes of metal speciation in Arctic lake in the zone of metallurgical waste and other areas, where natural processes prevail. Consecutive and parallel membrane filtration methods were used to compare of the results of water analysis in the Imandra lake. The membrane pore sizes were: 8 µm, 1.2 µm, 0.45 µm, 0.2 µm. The following filterates characteristics were used: (microfiltration-based) mechanical suspension and oxidized contaminants (>8 μm, 1.2 μm, 0.45 μm, 0.2 μm, 0.1 μm); and (ultrafiltration-based) colloid, bacteria, viruses, etc (less than 0.1 μm).</p><p>Industrial effluents lead to the formation of higher concentrations of elements (Ni, Cu, Pb) in their labile forms as were found. In the wastewater-mixing zone, the concentrations of most elements are evenly distributed in depth. In areas that are more distant, there was a significant increase in the concentration of elements in the near-bottom horizon in comparison with the surface waters (Fe by more than 3 times). The obtained results showed that numerous elements had diverse distribution by speciation in the point located closer to the source of wastewaters. This indicates a significant influence of adsorption process on the system balance by such elements as Fe, Cu, and rare earth elements.</p><p>The impact of the regional geochemical and anthropogenic speciation and the possible influence of the climatic factor on the metals speciation were showed.   The authors did not have data on the metals speciation in the chosen points for the whole period of monitoring from 1980 until present. However, ElementPhasMigration (certificate 2017662509, Dinu M.I.) software was used to calculate the shares of labile and non-labile metal speciation during the years of the highest pollution (beginning of the 1990s) and during the current period of the ecosystem restoration.    </p><p>The software used mathematic modeling of chemical reactions happening in the natural waters and was based on the main laws of analytical and physical chemistry: material balance equation, equilibrium constant, equations of electrical neutrality, equations of proton balance, and competing reactions.</p><p>On the one hand, the initial data comprised a significant number of physicochemical parameters of the environment (more than 10 metal ions, рН, content of organic and non-organic anions, etc.). On the other hand, it included diverse mathematical tools for consecutive calculation of acidity constant of organic acids, conditional constants of complexes stability, the share of strong and weak acids in the system, etc. The software solved the tasks on the evaluation of the metal speciation depending on the physical and chemical parameters of the environment and provided the data on the balance speciation of a wide spectrum of elements in the system. The final stage of the calculations included the results verification with the field data.      Financing RFS 18-77-00018</p>

scholarly journals Nagra/PSI Chemical Thermodynamic Data Base 01/01

2002 ◽  
Vol 90 (9-11) ◽  
Author(s):  
W. Hummel ◽  
U. Berner ◽  
E. Curti ◽  
F. J. Pearson ◽  
T. Thoenen
Keyword(s):  
Radioactive Waste ◽  
Data Base ◽  
Thermodynamic Data ◽  
Critical Appraisal ◽  
Fission Products ◽  
Performance Assessments ◽  
The Other ◽  
Chemical Thermodynamic ◽  
Carbonate Complexes

SummaryThe Nagra/PSI Chemical Thermodynamic Data Base has been updated to support performance assessments of the planned Swiss repositories for radioactive waste. The update from version 05/92 to 01/01 involved major revisions for most of the actinides and fission products. Altogether, more than 70% of the database contents have been revised. Data for U, Np, Pu, Am and Tc recommended by the NEA TDB project were considered in the update. Thermodynamic data for Th, Sn, Eu, Pd, Al, and solubility and metal complexation of sulphides and silicates were extensively reviewed. Data for Zr, Ni and Se were examined less rigorously as these elements are currently being reviewed in phase II of the NEA TDB project. Our experiences from this two year team effort can be summarised as follows. Detailed in-house reviews and critical appraisal of NEA recommendations greatly improved the chemical consistency and quality of the selected data. On the other hand, we could discern major gaps in the data, especially missing carbonate complexes. In some systems,

scholarly journals Status of fission fragment observables measured with the LOHENGRIN spectrometer

2019 ◽  
Vol 211 ◽  
pp. 04004 ◽  
Author(s):  
S. Julien-Laferrière ◽  
L. Thombansen ◽  
G. Kessedjian ◽  
A. Chebboubi ◽  
O. Serot ◽  
...  
Keyword(s):  
Fission Fragment ◽  
Isomeric Ratio ◽  
Nuclear Data ◽  
Nuclear Fission ◽  
Experimental Program ◽  
Spent Fuel ◽  
Reactor Physics ◽  
Model Calculations ◽  
Common Effort ◽  
Fission Yields

Nuclear fission yields are key parameters to evaluate reactor physics observables, such as fuel inventory, decay heat, spent fuel radiotoxicity, criticality but also for understanding the fission process. Despite a significant effort allocated to measure fission yields during the last decades, the recent evaluated libraries still need improvements in particular in the description of the uncertainties with the associated correlations. Additional kinds of measurements provide complementary information in order to test the models used in the nuclear data evaluation. Moreover, some discrepancies between these libraries must be explained. A common effort by the CEA, the LPSC and the ILL aims at tackling these issues by providing precise measurement of isotopic and isobaric fission yields with the related variance-covariance matrices. Nevertheless, the experimental program represents itself a large range of observables requested by the evaluations: isotopic yields, nuclear charge polarization, odd-even effect, isomeric ratio and their dependency with fission fragment kinetic energy as a probe of the nuclear de-excitation path in the (E*, Jπ) representation. Measurements for thermal neutron induced fission of 241Pu have been carried out at the Institut Laue Langevin using the LOHENGRIN mass spectrometer. Experimental program, observables reachable, results and comparison to model calculations are shown.

Revised Eh-pH Diagrams (25 C, One Bar) for Uranium and Transuranic Elements: Application to Radioactive Waste Studies

1988 ◽  
Vol 125 ◽  
Author(s):  
D. G. Brookins
Keyword(s):  
Radioactive Waste ◽  
Spent Fuel ◽  
Radionuclide Migration ◽  
Fuel Rods ◽  
Major Phase ◽  
Geochemical Behavior ◽  
Wide Range ◽  
Carbonate Complexes ◽  
Generic System ◽  
Very High

ABSTRACTEh-pH diagrams are useful for comparing the probable geochemical behavior of many elements including U and the transuranics Np, Pu, Am. Revised Eh-pH diagrams have been constructed for U, Np, Pu and Am at 25 C, 1 bar conditions. These diagrams, based on new and revised thermodynamic data, include aqueous and solid species in the generic system M-C-O-H. The species M(OH)− is considered herein, although it's existence has not been verified.Aqueous U(VI) species are dominated by below pH 5 and by carbonate complexes at higher pH. U(IV) species include important fields of UO2, and U(OH)4. If Si is present, USiO4 may be important. U3O8, occurs between the U(IV) and U(VI) species.Np(IV) solid species are problematic. NpO2 covers a wide range of Eh-pH, but its precursors, NpO. (OH)2 and Np(OH)4 cover more restrictive Eh-pH ranges with more important. This increases potential for radionuclide migration. Np(V, VI) carbonate complexes are important only at high Eh.Pu(IV) species are dominated by PuO2, but Pu(OH)4 does not occupy as much Eh-pH space, being replaced in large part by . With carbonate present, Pu(III) species also replace part of the Pu(OH)4 field, and Pu2 (CO3)3 becomes important. Pu(VI) carbonate complexess occur only at high Eh.Am(III) species dominate Eh-pH space in the system Am-C-O-H, with Am2 (CO3)3 a major phase. Under carbonate-poor conditions, Am(OH) 3 is important. AmO2 occurs at high Eh, pH, and at high Eh and very high pH.The importance of the M(OH)4 precursors to MO2 species is the enhanced possibility of radionuclide migration from buried spent fuel rods, even under reducing condtions.

Sign in / Sign up

Export Citation Format

Share Document