Polynuclear species of zirconium in acidic aqueous solution are investigated by combining X-ray absorption spectroscopy (XAFS) and nanoelectrospray mass spectrometry (ESI-MS). Species distributions are measured between pHC 0 and pHC 3 for [Zr]=1.5-10 mM. While the monomer remains a minor species, with increasing pH the degree of polymerization increases and the formation of tetramers, pentamers, octamers, and larger polymers is observed. The high resolution of the mass spectrometer permits the unambiguous determination of polynuclear zirconium hydroxide complexes by means of their isotopic patterns. The relative abundances of mononuclear and polynuclear species present simultaneously in solution are measured, even if one of the species contributes only 0.1% of the Zr concentration. For the first time it has been directly observed that the hydrolysis of polynuclear Zr species is a continuous process which leads to charge compensation through the sequential substitution of water molecules by hydroxide ligands until doubly charged polymers dominate at conditions (H+ and Zr concentrations) close to the solubility of Zr(OH)4(am). The invasiveness of the electrospray process was minimized by using very mild declustering conditions, leaving the polynuclear species within a solvent shell of approximately 20 water molecules.
Polynuclear hydroxide complexes play an important role for the hydrolysis of tetravalent thorium ions in aqueous solution, in particular for Th(IV) concentrations exceeding some [Th(IV)]=10
Polymerization in hexavalent uranium solutions was measured by electrospray ionization time-of-flight mass spectrometry in three different acidic media at pH values from 3 to 5.3 in order to detect all hydrolysis species present in solution. The aqueous solutions were directly measured without further dilution in organic solvents. At high uranyl concentrations ([U(VI)] = 10(- 3) M) artifacts were observed due to the presence of more than one solution species per formed microdroplet. Those artifacts were composed of ions and neutral species being present in the same droplet. However, by analyzing the detected species carefully, the origin of the artifacts could be traced back to the physically meaningful species. Still, only general trends of the hydrolysis behavior can be deduced from the measurements at [U(VI)] = 1 ⋅ 10(- 3) M. The solutions at [U(VI)] = 5 ⋅ 10(- 5) M did not show any comparable artifact formation. The detected species distributions resemble the expected trends calculated from the equilibrium constants published in the Nuclear Energy Agency Thermodynamic Database (NEA-TDB). The neutral (UO(2))(CO(3))(0) species present in solution causes, if located in the same microdroplet as a charged species, the apparent formation of dimeric and trimeric ternary hydroxo carbonate complexes at pH 5.3. As the uncharged species is not repelled from the ionic species, it might remain in the same droplet during the droplet fission process. By dividing those detected species into the uncharged (UO(2))(CO(3))(0) and a second ionic species, the relative abundances of the solution species can be corrected, leading to a good agreement with the predictions of the published equilibrium constants. In addition to the well-known trimer, we report the direct mass spectrometric detection of the dimeric (UO(2))(2)(OH)(2)(2+) species.
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