Vanadium(IV) and vanadium(V) complexation by succinic acid studied by affinity capillary electrophoresis. Simultaneous injection of two analytes in equilibrium studies.

The interaction of V(IV) and V(V) with succinic acid was investigated by affinity capillary electrophoresis (ACE) in aqueous acid solutions at pH values 1.5, 2.0 and 2.4, and different ligand concentrations. V(IV) and V(V) form protonated complexes with succinic acid ligand at this pH range. The logarithms of the stability constants, measured at 0.1 mol L-1 (NaClO4/HClO4) ionic strength and 25 °C, are logß111=7.4 ± 0.2 and logß122=14.1 ± 0.5 for V(IV), and logß111=7.3 ± 0.1 for V(V), respectively. The stability constant values, extrapolated to zero ionic strength with the Davies equation, are logß°111=8.3 ± 0.2 and logß°122=15.6 ± 0.5 for V(IV) and logß°111=7.9 ± 0.1 for V(V). The application of ACE to the simultaneous equilibria of V(IV) and V(V) (injection of two analytes) was also attempted. When the results were compared with those obtained when introducing only one analyte in the capillary, using the traditional version of the method, similar stability constants and precision are obtained. The possibility of studying two analytes simultaneously decreases the time needed for the determination of the constants; this feature is especially valuable when working with hazardous materials or when only small quantities of ligand are available.

Efficiency of dihydroxamic and trihydroxamic siderochelates to extract uranium and plutonium from contaminated soils.

Actinide-based mineral phases occurring in contaminated soils can be solubilized by organic chelators excreted by plants, such as citrate. Herein, the efficiency of citrate towards U and Pu extraction is compared to that of siderophores, whose primary function is the acquisition of iron(III) as an essential nutrient and growth factor for many soil microorganisms. To that end, we selected desferrioxamine B (DFB) as an emblematic bacterial trishydroxamic siderophore and a synthetic analog, abbreviated (LCy,Pr)H2, of the tetradentate rhodotorulic acid (RA) produced by yeasts. Firstly, the uranyl speciation with both ligands was assessed in the pH range 2-11 by potentiometry and visible absorption spectrophotometry. Equilibrium constants and absorption spectra for three [UO2(DFB)Hh](h-1)+ (h = 1-3) and five [UO2(LCy,Pr)lHh](2+h-2l)+ (-1 ≤ h ≤ 1 for l = 1 and h = 0-1 for l = 2) solution complexes were determined at 25.0 °C and I = 0.1 M KNO3. Similar studies for the Fe3+/(LCy,Pr)2- system revealed the formation of five species having [Fe(LCy,Pr)]+, [Fe(LCy,Pr)OH], [Fe(LCy,Pr)(OH)2]-, [Fe(LCy,Pr)2H], and [Fe2(LCy,Pr)3] compositions. Then, the ability of DFB, (LCy,Pr)H2, and citrate to solubilize either U or Pu from pitchblende-rich soils (soils 1 and 2) or freshly plutonium-contaminated soils (LBS and PG) was evaluated by performing batch extraction tests. U was extracted significantly only by citrate after a day. After one week, the amount of U complexed by citrate only slightly exceeded that measured for the siderochelates, following the order citrate > (LCy,Pr)H2 ≥ DFB ≈ H2O, and were comparatively very low. Pu was also more efficiently extracted by citrate than by DFB after a day, but only by a factor of ~2-3 for the PG soil, while the Pu concentration in the supernatant after one week was approximately the same for both natural chelators. It remained nearly constant for DFB between the 1st and 7th day, but drastically decreased in the case of citrate, suggesting chemical decomposition in the latter case. For the Fe-rich soils 1 and 2, the efficiencies of the three chelators to solubilize Fe after a day were of the same order of magnitude, decreasing in the order DFB > citrate > (LCy,Pr)H2. However, after a week DFB had extracted ~1.5 times more Fe, whereas the amount extracted by the other chelators stayed constant. For the less Fe-rich LBS and PG soils contaminated by Pu, the amounts of extracted Fe were higher, especially after 7 days, and the DFB outperformed citrate by a factor of nearly 3. The higher capacity of the hexadentate DFB to extract Pu in the presence of Fe and its lower ability to mobilize U qualitatively agree with the respective complexation constant ratios, keeping in mind that both Pu-containing soils had a lower iron loading. Noticeably, (LCy,Pr)H2 has roughly the same capacity as DFB to solubilize U, but it mobilizes less Fe than the hexadentate siderophore. Similarly, citrate has the highest capacity to extract Pu, but the lowest to extract Fe. Therefore, compared to DFB, (LCy,Pr)H2 shows a better U/Fe extraction selectivity and citrate shows a better Pu/Fe selectivity.

Assignment of complex species by affinity capillary electrophoresis: The case of Th(IV)-desferrioxamine B.

The electrophoretic mobility change of desferrioxamine B (DFO) was monitored by UV absorption spectrophotometry upon increasing the thorium(IV) concentration in the background electrolyte at two acidities ([HClO4 ]Tot = 0.0316 and 0.0100 M). These data enabled to assess the speciation model and to determine the equilibrium constant of [Th(DFO)H2 ]3+ at fixed ionic strength (I = 0.1 M (H,Na)ClO4 ). Affinity capillary electrophoresis (ACE) turned out to be most helpful in identifying the complexed species by ascertaining its charge and protonation state. The assignment of the correct stoichiometry relied on the reliable estimation of the electrophoretic mobility by assuming similar hydrodynamic radii for (DFO)H4+ and the chelate. The value of the apparent equilibrium constant (log ß112 = 38.7 ± 0.4) obtained by ACE compares favorably well with those reported in the literature for thorium and a range of other metal ions, according to a linear free-energy relationship. This method is useful for studying metal-ligand binding equilibria and provides valuable information for further modelling the behavior of tetravalent actinides under environmental conditions. Structural information about the prevalent solution species in acidic conditions was gained by DFT calculations, confirming the bishydroxamato coordination mode of Th4+ by the diprotonated ligand.

Interdisciplinary Round-Robin Test on Molecular Spectroscopy of the U(VI) Acetate System.

A comprehensive molecular analysis of a simple aqueous complexing system-U(VI) acetate-selected to be independently investigated by various spectroscopic (vibrational, luminescence, X-ray absorption, and nuclear magnetic resonance spectroscopy) and quantum chemical methods was achieved by an international round-robin test (RRT). Twenty laboratories from six different countries with a focus on actinide or geochemical research participated and contributed to this scientific endeavor. The outcomes of this RRT were considered on two levels of complexity: first, within each technical discipline, conformities as well as discrepancies of the results and their sources were evaluated. The raw data from the different experimental approaches were found to be generally consistent. In particular, for complex setups such as accelerator-based X-ray absorption spectroscopy, the agreement between the raw data was high. By contrast, luminescence spectroscopic data turned out to be strongly related to the chosen acquisition parameters. Second, the potentials and limitations of coupling various spectroscopic and theoretical approaches for the comprehensive study of actinide molecular complexes were assessed. Previous spectroscopic data from the literature were revised and the benchmark data on the U(VI) acetate system provided an unambiguous molecular interpretation based on the correlation of spectroscopic and theoretical results. The multimethodologic approach and the conclusions drawn address not only important aspects of actinide spectroscopy but particularly general aspects of modern molecular analytical chemistry.

Affinity capillary electrophoresis in studying the complex formation equilibria of radionuclides in aqueous solutions.

Interaction of radionuclides with inorganic and organic species present in natural environment plays an important role in their eventual dispersion. The complex equilibria established in the aqueous phase cause significant changes in the migration properties of radionuclides. Affinity capillary electrophoresis (ACE) can be fruitful in studying these equilibria. This paper reviews the recent methodological advances of the use of ACE in studying the complex equilibria of radionuclides in aqueous solutions. Special attention is paid to the determination of a number of species involved in equilibrium, species constituents (number of ligands, protonated, deprotonated), the influence of ionic strength and temperature on stability constants of complex species formed. Use of ACE for the determination of the main thermodynamic parameters (the molar Gibbs energy (Δr Gm ), the molar enthalpy (Δr Hm ) and the molar entropy (Δr Sm )) of complex formation reactions is also discussed. These data are essential to predict dispersion of radionuclides in the natural environment.

Uranyl complexation with acetate studied by means of affinity capillary electrophoresis.

The interaction of uranyl with acetate is studied by affinity capillary electrophoresis in aqueous acid solutions at the pH values 2.0 and 2.5. The use of data on metal ion mobilities at different pHs allows to establish the ligand species interacting with metal ion and complex species formed. The formation of two complex species UO2CH3COO(+) and UO2(CH3COO)2 is observed (acetic acid concentration is up to 0.8M). In the case of uranyl-acetic acid system, the viscosity of solution is significantly changed with an increase of acid concentration. For calculation of ion mobilities the viscosity changes are taken into account. The stability constants are calculated at the ionic strengths 0.02 and 0.05 mol L(-1). The logarithms of the thermodynamic stability constants (ß°) calculated with Davies equation for the activity coefficients of the ions are log ß1(°)=2.94±0.08 and log ß2(°)=5.50±0.15 at 25 °C. Obtained values are compared with literature data.

Uranyl complexation with selenate at variable temperatures studied by affinity capillary electrophoresis.

The uranyl-selenate system is studied in aqueous acid solutions (pH 2.5) at different values of the ionic strength (from 0.02 to 0.1 molL(-1)) in the temperature range from 15°C to 55°C by affinity capillary electrophoresis. Hydrodynamic transfer of the sample through the non-thermostated inlet into the thermostated region of capillary is used to avoid the influence of non efficiently thermostated short inlet. The formation of two complex species UO(2)SeO(4) and UO(2)(SeO(4))(2)(2-) is observed. Thermodynamic parameters (the molar Gibbs energy of reaction (Δ(r)G(m)), the molar enthalpy of reaction (Δ(r)H(m)) and the molar entropy of reaction (Δ(r)S(m))) are calculated and extrapolated to zero ionic strength with aid of specific ion interaction theory. Results show that complex species of uranyl with selenate become stronger as the temperature is increased. The complexation is endothermic and entropy-driven, showing typical characteristics of inner-sphere complexation between hard acceptor and hard donor.

Effect of non-thermostated capillary inlet in affinity capillary electrophoresis: uranyl-selenate system at variable temperatures.

The influence of non-thermostated capillary inlet on accuracy of data obtained by affinity capillary electrophoresis is examined in the case of kinetically labile systems (with fast kinetics of equilibrium) at different temperatures. The system uranyl-selenate is studied in aqueous perchloric acid solutions (pH 2.5, ionic strength 0.05 mol l(-1)) in the temperature range from 15 °C to 55 °C. Moving of the sample through the non-thermostated inlet into the thermostated region of the capillary is used in order to avoid the influence of non efficiently thermostated short capillary inlet. The data on mobility values of uranyl and the values of stability constants obtained by this mode are compared with the data obtained in a traditionally used mode (injection in non-thermostated inlet region). The uranyl mobility values obtained by the two methods are different at temperature higher than 35 °C. However, the difference between stability constants obtained by the two methods is not significant (ambient temperature is 20 °C).

Capillary zone electrophoresis for U(VI) and short chain carboxylic acid sorption studies on silica and rutile.

Capillary zone electrophoresis was used to study the uranyl and short chain carboxylic acid sorption on silica and rutile. The separation and the simultaneous determination (in a single run) of a number of short chain carboxylic acids (oxalic, formic, acetic and propionic) and U(VI) with direct UV detection is developed for the analysis of solutions after the sorption experiments. The reverse polarity mode is used (the injection is performed at the negative end). The matrix effect of Si(IV) (possible silica dissolution product) and perchlorate (added for constant ionic strength in sorption experiments) on the separation of U(VI) and organic acids is investigated. The influence of methanol addition in carrier electrolyte on the separation selectivity of given analytes is also studied. Under the chosen conditions (carbonate buffer (ionic strength of 0.1M), pH 9.8, 0.15 mM of tetradecyltrimethylammonium bromide, 25% (v/v) of methanol) the calibration curves are plotted. They are linear in two ranges of concentration from ∼1×10(-5) to ∼1×10(-3) M for oxalate, acetate, propionate, U(VI) and ∼1×10(-4) to ∼1×10(-3) for formate. The accuracy of the procedure is checked by the "added-found" method in simulation solutions. The relative standard deviations of the concentrations found are within the range of 1-10% and the recovery is in the range of 90-115%. This method is applied for the analysis of aqueous samples issued from sorption experiments on silica and rutile. The obtained results indicate that the given organic acids decrease uranium sorption both on silica and rutile. These experiments demonstrate that short chain carboxylic acids can influence the mobility and the chemistry of U(VI) in the environment.

Interaction of uranyl with Se(IV) and Se(VI) in aqueous acid solutions by means of capillary electrophoresis.

The uranyl-selenium(IV) and uranyl-selenium(VI) interactions were studied by CE in aqueous acid solutions, containing U(VI) and Se(IV) or Se(VI) at different concentrations, at pH 1.5, 2.0 and 2.5. The method proposed in this paper allows one with the use of CE data on metal ion mobilities at different pHs to establish the ligand species interacting with metal ion and complex species formed. In the case of Se(VI) a selenate, as demonstrated, interacts with uranyl ions, in the case of Se(IV) this is a hydroselenite. It was also shown that the equilibria for the U(VI)-Se(VI) and U(VI)-Se(IV) systems can be established from CE data. The formation of UO(2)SeO(4), UO(2)(SeO(4))(2) (2-), UO(2)HSeO(3) (+) and UO(2)(HSeO(3))(2) species is demonstrated. The stability constant values were measured at different ionic strengths (from 0.02 to 0.2 mol/L). The logarithms of the stability constant values (ß°) extrapolated to ionic strength 0 by the specific ion interaction theory (SIT) are found to be log ß°(1) = 2.93 ± 0.06 for UO(2)SeO(4) formation, log ß°(2) = 4.030.18 for UO(2)(SeO(4))(2) (2-) formation, log ß°(1) = 3.270.15 for UO(2)HSeO(3) (+) formation and log ß°(2) = 5.510.11 for UO(2)(HSeO(3))(2) at 25°C. The results for the first constant values for each of systems are consistent with the published values. For UO(2)(SeO(4))(2) (2-) formation, a new constant stability value is given. The existence of UO(2)(HSeO(3))(2) complex species is demonstrated and its constant stability value is given for the first time.

Uranyl-Se(IV) interaction in aqueous acid solutions studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS) and UV-Vis spectrophotometry.

The uranyl-selenium(IV) interaction was studied by time-resolved laser-induced fluorescence spectroscopy in aqueous perchloric acid solutions containing 1 x 10(-4) M U(VI) and Se(IV) at different concentrations (from 0 up to 0.3 M) at pH 1 and 2. The quenching of uranyl fluorescence is observed. HSeO(3)(-) is demonstrated to be responsible for the fluorescence quenching. Stern-Volmer analysis gives the dynamic quenching rate constant value (k(q)) (5.0 +/- 0.4) x 10(9) L M(-1) s(-1) at ionic strength (mu) 0.05 M. The bimolecular excited-state process is shown to be diffusion-controlled as k(q) is practically identical to the diffusion rate constant as calculated for uranyl and hydroselenite charged species. With an increase of HSeO(3)(-) concentration, static quenching occurs in addition to the dynamic quenching. The hypothesis of the formation of a weak fluorescent ground state complex between uranyl and HSeO(3)(-) is supported. The logarithm of the stability constant value (beta) is found to be 3.35 +/- 0.12 (mu= 0.05 M) and 3.32 +/- 0.15 (mu = 0.2 M). These constants are confirmed by UV-Vis spectrophotometry. The modelling factor analysis of absorption spectra gives logbeta = 3.35 +/- 0.17 (mu = 0.035 M). Extrapolation to mu = 0 by the specific ion interaction theory (SIT) gives logbeta degrees = 3.62 +/- 0.15 at 20 degrees C.

Simultaneous determination of uranium carbide dissolution products by capillary zone electrophoresis.

Separation and simultaneous determination of a number of organic acid anions (oxalate, mellitate, trimellitate and benzoate) and U(VI) with direct UV detection is developed for analysis of uranium carbide (UC) dissolution products by capillary zone electrophoresis (CZE). Reverse polarity mode is used. It is found that complex formation of U(VI) with carbonate, used as a carrier electrolyte, allows U(VI) to be determined, as negatively charged species, in a single run with organic acid anions. Some parameters such as pH value, composition of electrolyte and detection wavelength are optimized. Under the chosen conditions (carbonate buffer (ionic strength of 100 mM), pH 9.8, 0.15 mM tetradecyltrimethylammonium bromide (TTAB)) a complete separation is achieved. Calibration plots are linear in two ranges of concentration for U(VI) ( approximately 1 x 10(-5) to 1 x 10(-3)), mellitate and trimellitate ( approximately 5 x 10(-6) to 5 x 10(-4)), and about one range ( approximately 1 x 10(-4) to 5 x 10(-3)) for oxalate and benzoate. Accuracy of the procedure is checked by the "added-found" method in standard mixture solutions. Relative standard deviation is within the range of 2-10% and the recovery is in the range of 90-110%. This method is applied for the analysis of real UC dissolution samples.

Application of capillary electrophoresis for inorganic selenium speciation in the frame of high-level waste management.

Capillary electrophoresis (CE) with direct UV detection is proposed for speciation of inorganic Se in high-level liquid waste. In this aim, the optimal conditions of measurements (pH, electrolyte buffer concentration) and the influence of nitrate excess on the quantitative determination of Se(IV) and Se(VI) were studied. Different electrolyte buffers were considered: carbonate, phosphate and citrate. It was found, that citrate buffer is the most suitable for the application under consideration. Under the chosen optimal conditions (20 mmol L(-1) citrate buffer, pH 2.5), calibration curves for Se(IV) and Se(VI) are linear in the concentration range 10(-4)-10(-3) mol L(-1). The detection limits are 4x10(-6 )for Se(IV) and 2x10(-5) for Se(VI). The accuracy of the procedure was checked by calculating the recovery by spiking simulation solutions. Relative standard deviation (S(r)) is less than 10%.

Copper-mercury film electrode for cathodic stripping voltammetric determination of Se(IV).

The copper-mercury film electrode has been suggested for the determination of Se(IV) in a wide range of concentration from 1x10(-9) to 1x10(-6) mol L(-1)by square-wave cathodic stripping voltammetry. Insufficient reproducibility and sensitivity of the mercury film electrode have been overcome by using copper(II) ions during the plating procedure. Copper(II) has been found to be reduced and form a reproducible copper-mercury film on a glassy carbon electrode surface. The plating potential and time, the concentration of copper(II) and the concentration of the supporting electrolyte have been optimised. Microscopy has been used for a study of the morphology of the copper-mercury film. It has been found that it is the same as for the mercury one. The preconcentration step consists in electrodeposition of copper selenide on the copper-mercury film. The relative standard deviation is 4.3% for 1x10(-6) mol L(-1) of Se(IV). The limit of detection is 8x10(-10) mol L(-1) for 5 min of accumulation.