Search Results
You are looking at 1 - 10 of 26 items for
- Author or Editor: G. Choppin x
- Refine by Access: All Content x
Abstract
A stopped-flow rapid mixing device interfaced to a high performanceminiature fibre optic CCD NIR detector permits the study of fast redox kineticsof actinide reactions at minimal cost. The use of fibre optics enables thestopped-flow device to be readily used in a glove-box. The system has beenevaluated at 980 nm by observing the in-growth of Np(V) from a fast reductionreaction of Np(VI), and has been shown to perform well in this spectral region.
Abstract
Data on the stability of Pu(V) as the dominant oxidation state of tracer concentrations of plutonium in natural waters is reviewed. Laboratory experiments for solutions of 0.1 and 1.0M (NaCl) ionic strength and pH 3–10 confirm the dominance of Pu(V) as the state in solution. Humics in the waters can cause reduction to Pu(IV).
Abstract
Nuclear test explosions and nuclear reactor wastes and accidents have released large amounts of radioactivity into the environment. Actinideions 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)O2 + and Pu(V)O2 +, the most significant soluble states in natural oxic waters, are relatively noncomplexing and resistant to hydrolysis and subsequent precipitation. The solubility of NpO2 + can be as high as 10−4M while that of PuO2 + is much more limited by reduction to the insoluble tetravalent species, Pu(OH)4, (pKsp≥56) but which can be present in the pentavalent form in aqautic phases as colloidal material. The solubility of hexavalent UO2 2+ in sea water is relatively high due to formation of carbonate complexes. The insoluble trivalent americium hydroxocarbonate, Am(OH)(CO3) 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 needed to allow proper and reliable modeling needed for disposition of nuclear waste over many thousands of years.
Abstract
Stability constants (log b101) of Th4+, UO2 2+, NpO2 + and Am3+ with [NaP5W30O110]14- were determined by solvent extraction (m = 0.1M NaCl) and found to be 6.18±0.07, 3.80±0.06, 2.98±0.04, and 5.85±0.05, respectively. The order of stability constants: Th4+>Am3+>UO2 2+>NpO2 + is due to electrostatic repulsion between the actinyl oxygens and oxygens on the polyoxometalate surface. The order of stability constants for metal complexes with [P2W18O62]6- is Th4+>UO2 2+>Eu3+>NpO2 + because the steric repulsion between actinyl oxygens and oxygens on polyoxometalate are less important. Enthalpies of complexation were measured by calorimetric titration of Th4+, UO2 2+, Nd3+ with [NaP5W30O110]14- and [P2W18O62]6-. The results indicate that the conformation and charge distribution of the microscopic surface structures are important factors in the formation of pseudocolloids.
Abstract
Actinide(III), (IV), (V) and (VI) ions were extracted by N,N
-dimethyl-N,N-dihexyl-3-oxapentanediamide (DMDHOPDA) and thenoyltrifluoroacetone (HTTA). The extraction behaviors suggested the possibility of the mutual separation, and the convenient separation method of actinide ions (III), (IV), (V) and (VI) without reducing and oxidizing agents was studied. Th(IV) was extracted from the aqueous phase by HTTA (5 mM in toluene) in the first step. The Am(III) and U(VI) ions can be extracted by 1 and 20 mM DMDHOPDA in toluene, and the Np(V) ion can be extracted into nitrobenzene with 100 mM DMDHOPDA in the last step. The residual activities in the aqueous phase were much lower than the initial activities. These activities in the fractions were confirmed by the gamma- and the alpha-spectrometry. The one-through and rough separation is advanced, and in case of the fine isolation of actinide elements, each fraction should be purified in more detail.
Abstract
The diamide, N,N
-dimethyl-N,N-dihexyl-3-thiopentanediamide (DMDHTPDA) was synthesized and thested for extraction of Eu(III), Am(III), Th(IV) and U(VI). DMDHTPDA shows a very weak complexation with these metal ions, which can be attributed to the soft base nature of the sulfur atom. None of the cations were extracted into the organic phase when DMDHTPDA alone was present. Synergistic extraction was measured for DMDHTPDA plus thenoyltrifluoroacetone. From the extraction dependencies on pH and extractant concentration, formation of mixed TTA+DMDHTPDA complexes were indicated. Except for the Th(IV) system, the separation and synergistic factors were smaller for the TTA+DMDHTPDA extractant than for the system of TTA+DMDHOPDA (the oxo ether analog of DMDHTPDA).
Abstract
The extraction of UO 2 2+ , Am3+, and Th4+ by 1-phenyl-3-methyl-4-benzylpyrazolone with crown ethers was studies using 0.1M (NaClO4) aqueous phase and toluene. The crown ethers were 12C4, 15C5, 18C6, DB18C6 and DCH18C6. The synergic equilibrium constant did not show correlation between the cationic radii and the ether cavity size nor did the values follow a simple order of ether basicity. The ether basicity, steric effects, and the number of ether oxygens bound to the cation are the combined factors which seemingly determine the pattern of M(PMBP)n—CE interaction.
Abstract
N,N
-dimethyl-N,N-dihexyl-3-oxapentanediamide, DMDHOPDA, N,N-dihexyl-3-thiopentanediamide, DHTPDA and N,N-dihexyl-3-oxapentanediamide, DHOPDA were synthesized and tested for the synergistic extraction of Eu3+, Th4+, UO
2
2+
, NpO
2
+
and Am3+ with thenoyltrifluoroacetone (HTTA). Although Eu3+, Th4+, UO
2
2+
and Am3+ were not extracted by DHTPDA or DHOPDA alone, they were extracted synergistically when combined with HTTA. Analysis of the dependency of extraction on pH and extractant concentration indicated that the dominant extracted species were Eu(TTA)3(A), Th(TTA)3(A)(X), UO2(TTA)2(A) and Am(TTA)3(A) (where A is diamide, and X is chloroacetate or ClO
4
–
).
Abstract
The effects of ionic strength and of ethylenediamin et etraacetic acid (EDTA) on the sorption of uranyl ion, UO2 2+, to SiO2·xH2O (silica gel) were investigated. It was observed that pH and the ions present in the supporting electrolytes influence the ionic strength effects. The presence of different sodium salts in the concentration range (0.20 to 1.40M) suppressed the sorption of UO2 2+ in the order: NaNO3 < NaClO4 < NaCl < NaOCOCH3 < Na2SO4 [pH 2.75(±0.05)], while the presence of perchlorate salts of Li+, Na+ and Ca2+ (0.20 to 1.40M) promoted the sorption of UO2 2+ on silica gel in the order: LiClO4∼NaClO4<Ca(ClO4)2 at pH 2.80(±0.05). The ionic strength effect on UO2 2+ sorption was studied in presence of EDTA (0–1.00·10−3M) in the pH range 2.90 to 5.57. The sorption data and speciation calculation suggest negligible complexation of UO2 2+ with EDTA at I≥1.00M NaClO4.
Abstract
This paper describes the technical issues involved in the development of a feasible solution toward permanent radioactive waste disposal. Recent progress on internationally collaborative research efforts concerning the multibarrier concept, in situ experiments, computer modeling and natural analogues are discussed.
