Thermodynamic Study of Am(III)-Isosaccharinate Complexation at Various Temperatures Implicating a Stepwise Reduction in Binding Denticity.

Isosaccharinic acid, a major final product of cellulose degradation under highly alkaline cement porewater conditions, is known to increase the mobility of actinides via strong complex formation. In this study, the formation of Am(III) complexes with α-d-isosaccharinate (ISA) was studied in terms of thermodynamics and coordination structures by combining spectrophotometry, time-resolved laser fluorescence spectroscopy (TRLFS), and density functional theory (DFT) calculations. The formation constants of the Am(III)-ISA complexes were determined by absorption spectroscopy at temperatures in the range of 15-70 °C. The measured reaction enthalpy and entropy changes indicate that the formation of a 1:1 Am(III)-ISA complex is driven by an increase in entropy. By contrast, the 1:2 complex formation is exothermic with a much less increase in entropy. DFT calculations predict that C2- and C4-hydroxyl groups, along with the carboxyl group, participate in the tridentate chelate binding of the primary ISA. The thermodynamic, TRLFS, and DFT results collectively suggest the tridentate binding of the primary ISA to Am(III) via a carboxylate and C2- and C4-hydroxyl groups in the protonated state and reduced dentate binding of the secondary ISA, such as bidentate binding, forming a four-membered ring structure via the carboxylate group.

Thermodynamic Studies on the Hydrolysis of Trivalent Plutonium and Solubility of Pu(OH)3(am).

The temperature-dependent reaction properties of actinide elements are of particular interest in the safety assessment of high-level radioactive waste (HLRW) disposal systems. In this study, the hydrolysis of Pu(III) and the solubility of Pu(OH)3(am) were investigated at various temperatures (10-40 °C) in 0.1 M NaClO4. A strong reducing condition for maintaining the oxidation state of Pu(III) while slowly increasing the pH of the solution was realized by electrolysis. The formation constants of the first hydrolysis species, log *ß1', and the solubility products of Pu(OH)3(am), log *Ks,0', at 10, 17, and 40 °C were experimentally determined using spectrophotometry, laser-induced breakdown detection, and radiometry. The enthalpy and entropy changes for these reactions were estimated using the van't Hoff equation. The first hydrolysis of Pu(III) is endothermic (ΔrHm° = 34.10 ± 4.48 kJ mol-1), and the dissolution of Pu(OH)3(am) is exothermic (ΔrHm° = -294.29 ± 23.05 kJ mol-1) with negative entropy changes. These thermodynamic data will contribute to improving the reliability of the safety assessment of HLRW disposal facilities and understanding the geochemical behavior of Pu under reducing or anoxic aqueous conditions at elevated temperatures.

Structural and spectroscopic studies of spontaneously formed crystalline Eu(iii)-aliphatic dicarboxylates at room temperature.

Complexation of actinides and lanthanides with carboxylic organic ligands is a critical issue affecting radionuclide migration from deep geological disposal systems of spent nuclear fuel. A series of Eu(iii)-aliphatic dicarboxylate compounds, as chemical analogs of radioactive Am(iii) species, Eu2(Ox)3(H2O)6, Eu2(Mal)3(H2O)6, and Eu2(Suc)3(H2O)2, were synthesized and characterized using X-ray crystallography and time-resolved laser fluorescence spectroscopy to examine the ligand-dependent binding modes and the corresponding changes in spectroscopic properties. Powder X-ray crystallography results confirmed that all of the compounds presented a crystalline polymer structure with a trigonal prism square-face tricapped polyhedron geometry centered on Eu(iii) in a nine-coordinate environment involving nine oxygen atoms. This study captures the transition of the coordination modes of aliphatic dicarboxylate ligands from side-on to end-on binding as the carbon chain length increases. This transition is illustrated in malonate bindings involving a combination of side-on and end-on modes. Strongly enhanced luminescence, especially for the hypersensitive peak, indicates a low site symmetry in the formation of solid compounds. The number of remaining bound water molecules was estimated from the resultant increased luminescence lifetimes, which were in good agreement with crystal structures. The excitation-emission matrix spectra of these crystalline polymers suggest that Ox ligands promote the sensitized luminescence of Eu(iii), especially in the UV region. In the case of Mal and Suc ligands, charge transfer occurs in the opposite direction from Eu(iii) to the ligands under UV excitation, resulting in weaker luminescence.

Study of Aqueous Am(III)-Aliphatic Dicarboxylate Complexes: Coordination Mode-Dependent Optical Property and Stability Changes.

The thermodynamics of Am(III) complex formation in natural groundwater systems is one of the major topics of research in the field of high-level radioactive waste management. In this study, we investigate the absorption and luminescence properties of aqueous Am(III) complexes with a series of aliphatic dicarboxylates in order to learn the thermodynamic complexation behaviors in relation to binding geometries. The formation of Am(III) complexes with these carboxylate ligands induced distinct red shifts in the absorption spectra, which enabled chemical speciation. The formation constants determined by deconvolution of the absorption spectra showed a linear decrease for the three ligands (oxalate (Ox), malonate (Mal), and succinate (Suc)) and a mild decrease for the remaining ligands (glutarate (Glu) and adipate (Adi)). Time-resolved laser fluorescence spectroscopy (TRLFS) was used to obtain information about the aqua ligand, which indirectly indicated the bidentate bindings of these dicarboxylate ligands. A complementary attenuated total reflectance Fourier transform infrared (ATR-FTIR) study on Eu(III), which is a nonradioactive analogue of Am(III) ion, showed that the coordination modes differ depending on the alkyl chain length. Ox and Mal bind to Am(III) via side-on bidentate bindings with two carboxylate groups, resulting in the formation of stable 5- and 6-membered ring structures, respectively. On the other hand, Suc, Glu, and Adi form end-on bidentate bindings with a single carboxylate group, resulting in a 4-membered ring structure. Density functional theory calculations provided details about the bonding properties and supported the experimentally proposed coordination geometries. This study demonstrates that coordination mode-dependent changes in optical properties occur along with thermodynamic stability changes in Am(III)-dicarboxylate complexes.

Visible-NIR absorption spectroscopy study of the formation of ternary plutonyl(VI) carbonate complexes.

We present the first experimental evidence for the ternary complexation of calcium and magnesium ions with plutonyl(vi)tricarbonate species in carbonate-containing aqueous solutions using visible-NIR spectrophotometric titration. Prior to studying the ternary plutonyl(vi) carbonate complexation, visible-NIR absorption spectral information of PuO2(CO3)22- and PuO2(CO3)34- was successfully obtained. PuO2(CO3)22- has a prominent peak at 853 nm and its molar absorptivity was determined to be ε853, PuO2(CO3)22- = 49.0 ± 4.2 M-1·cm-1. The spectrophotometric titration results by adding calcium or magnesium to the plutonyl(vi) carbonate system consisting of PuO2(CO3)22- and PuO2(CO3)34- indicate the formation of CaPuO2(CO3)32- and MgPuO2(CO3)32- complexes and provide the formation constants at 0.1 M H/NaClO4 for MPuO2(CO3)32- from PuO2(CO3)34-, log K = 4.33 ± 0.50 and 2.58 ± 0.18 for M = Ca2+ and Mg2+, respectively. In addition, the formation constants of CaPuO2(CO3)32- and MgPuO2(CO3)32- from PuO2(CO3)34- at infinite dilution (log K°) were proposed to be 6.05 ± 0.50 and 4.29 ± 0.18, respectively, based on the correction of ionic strength using the Davies equation. The absorption spectrum of the ternary plutonyl(vi) complexes of CaPuO2(CO3)32- is similar to that of PuO2(CO3)34- with the exception of a characteristic absorption peak at 808 nm (ε808, CaPuO2(CO3)32- = 42.9 ± 1.6 M-1·cm-1). According to the calculated aqueous plutonyl(vi) speciation including the ternary plutonyl(vi) complexes, CaPuO2(CO3)32- is considered the dominant Pu(vi) species under environmental conditions, and plutonyl(vi) may be more mobile than expected in previous assessments.

Studies of aqueous U(iv) equilibrium and nanoparticle formation kinetics using spectrophotometric reaction modeling analysis.

Hydrolysis of tetravalent uranium (U(iv)) and U(iv)-nanoparticle formation kinetics were examined over a wide range of temperatures using spectrophotometric reaction modeling analysis. The characteristic absorption bands representing U4+, U(OH)3+, and a proposed oxohydroxo species were newly identified in the UV region (190-300 nm). Dynamic absorption band changes in the UV and visible regions (360-800 nm) were explored to reevaluate the binary ion interaction coefficients for U(iv) ions and the thermodynamic constants of the primary hydrolysis reaction, including complexation constants, enthalpy, and entropy. No further hydrolysis equilibrium beyond the formation of U(OH)3+ was identified. Instead, an irreversible transformation of U(iv) ions to U(iv)-nanoparticles (NPs) was found to occur exclusively via the formation of a new intermediate species possessing characteristic absorption bands. The kinetic analysis, based on a two-step, pseudo-first-order reaction model, revealed that the rate of the initial step producing the intermediates is highly temperature-dependent with the measured kinetic energy barrier of ∼188 kJ mol-1. With additional experimental evidence, we conclude that the intermediates are oligomeric oxohydroxo U(iv) species occurring from the condensation of U(iv) ions and simultaneously participating in the nucleation and growth process of UO2(cr)-NPs.

Hydrolysis of trivalent plutonium and solubility of Pu(OH)3 (am) under electrolytic reducing conditions.

The aim of this work is to determine the solubility product of plutonium hydroxide under reducing conditions and to ascertain the stability of Pu(OH)3 (am) in water. Hydrolysis of Pu(iii) and solubility of Pu(OH)3 (am) were investigated at a constant ionic strength of 0.1 M NaClO4. Coulometric titration was adopted to adjust the pH of plutonium solutions, during which the electrolytic reducing conditions maintained the oxidation state of Pu(iii). Chemical speciation for dissolved plutonium was investigated using sensitive spectrophotometry coupled with a liquid waveguide capillary cell. The spectroscopic investigations indicated that dissolved Pu(iv), Pu(v), and Pu(vi) species were ignorable under these experimental conditions. The absorbance of Pu3+ ions decreased due to hydrolysis of Pu(iii) but the absorbance of Pu(iii) hydrolysis species was not distinguishable. The formation constant for the first hydrolysis species (log *ß'1) determined in the present study is -6.62 ± 0.25. The non-crystalline structure of the plutonium precipitate was observed through X-ray diffraction. The solubility product of Pu(OH)3 (am), log *K's,0 is determined to be 15.23 ± 0.50. These results indicate a stronger tendency for the hydrolysis of Pu(iii) and higher stability (lower solubility) of Pu(OH)3 (am) compared to Am(iii).

Quantitative analysis of uranium in aqueous solutions using a semiconductor laser-based spectroscopic method.

A simple analytical method based on the simultaneous measurement of the luminescence of hexavalent uranium ions (U(VI)) and the Raman scattering of water, was investigated for determining the concentration of U(VI) in aqueous solutions. Both spectra were measured using a cw semiconductor laser beam at a center wavelength of 405 nm. The empirical calibration curve for the quantitative analysis of U(VI) was obtained by measuring the ratio of the luminescence intensity of U(VI) at 519 nm to the Raman scattering intensity of water at 469 nm. The limit of detection (LOD) in the parts per billion range and a dynamic range from the LOD up to several hundred parts per million were achieved. The concentration of uranium in groundwater determined by this method is in good agreement with the results determined by kinetic phosphorescence analysis and inductively coupled plasma mass spectrometry.

Evaluation of the behavior of uranium peroxocarbonate complexes in Na-U(VI)-CO3-OH-H2O2 solutions by Raman spectroscopy.

In this work, the formation of uranium species and their stabilities in Na-U(VI)-CO(3)-OH-H(2)O(2) solutions at different pHs are studied by Raman spectroscopy. In this solution, the UO(2)(O(2))(CO(3))(2)(4-) species was formed together with three other uranium species of UO(2)(O(2))(2)(2-), UO(2)(CO(3))(3)(4-), and a speculated uranium species of the uranyl carbonate hydroxide complex, UO(2)(CO(3))(x)(OH)(y)(2-2x-y), which showed remarkable Raman peaks at approximately 769, 848, 811, and 727 cm(-1), respectively. The UO(2)(O(2))(CO(3))(2)(4-) species disappeared at pH conditions where bicarbonate dominated, and its Raman peak could be clearly observed in only a narrow pH range from approximately 9 to 12. When the pH of the solution increased further, the UO(2)(O(2))(CO(3))(2)(4-) species changed to UO(2)(CO(3))(3)(4-) and the UO(2)(CO(3))(x)(OH)(y)(2-2x-y) species. Moreover, the UO(2)(O(2))(CO(3))(2)(4-) species continuously decomposed into uranyl tricarbonate in the carbonate solution at an elevated temperature because of the instability of the peroxide ion, O(2)(2-), in alkaline conditions.

Detection method for ionic species based on the electroacoustic effect.

The development and application of a new ion detection method based on the electroacoustic (EA) effect is described. An EA signal, produced by applying a pulsed-type electric field to an electrolyte solution in an electroacoustic cell, is dependent on the electrical and thermal properties of the electrolyte and can be detected by using a conventional gas microphone system. The EA signals, generated in this fashion, are proportional to the square of the amplitude of the pulsed-type electric field and show an inverse dependence on the modulated frequency, as found in other acoustic detection systems. The results of this study demonstrate that the EA signals observed with the new system display a linear dependence on the concentration of the electrolyte over a 3 order-of-magnitude concentration range (ca. 10(-7)-10(-4) M). The detection limit of this system was shown to be as low as 29.9 ppb for an aqueous solution of HCl. The results also indicate that the EA signal is proportional to the equivalent conductivity of electrolytes in aqueous solution. As a consequence, the new method has the potential of being used as a universal detector for ions in solutions. An important property of this detection system is that it can be applied to in situ ion detection, and as a result, it can be employed in kinetic studies to follow the progress of ionic chemical reactions.

Combined LIBD and XAFS investigation of the formation and structure of Zr(IV) colloids.

The solubility of Zr(OH)4(am)--in other words hydrated Zr(IV) oxyhydroxide--is determined by means of coulometric titration (CT), and colloids are detected by laser-induced breakdown when the solubility limit is exceeded. Our results at pH 3-8 demonstrate that the solubility of Zr(OH)4(am) is several orders of magnitude higher than reported classical solubility data for acidic solutions, determined from undersaturation with a less soluble microcrystalline Zr(IV) oxide precipitate. Analysis of extended X-ray absorption fine structure (EXAFS) data shows that the microcrystalline colloids in a 0.1 mol l(-1) Zr aqueous solution at pH 0.2 contain tetrameric units, similar to those present in the structure of ZrOCl2.8H2O. Characterization of the CT solutions by means of EXAFS shows that oligomeric species form as the solubility limit is approached. The current lack of data on equilibrium constants for polynuclear hydroxide complexes prohibits the use of a realistic speciation model to describe the solubility of pH-dependent Zr(OH)4(am). However, the solubility curve is obtained using the mononuclear hydrolysis constants estimated in the present paper, along with the solubility constant (log K'sp=-49.9+/-0.5 in 0.5 mol l(-1) NaCl; log K degrees(sp)=-53.1+/-0.5 at I=0).