TY - JOUR

T1 - On the polymerization of hexavalent uranium. An electrospray mass spectrometry study

AU - Steppert, Michael

AU - Walther, Clemens

AU - Fuss, Markus

AU - Büchner, Stefanie

PY - 2012/2/10

Y1 - 2012/2/10

N2 - 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 (UO2)2(OH)22+ species.

AB - 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 (UO2)2(OH)22+ species.

UR - http://www.scopus.com/inward/record.url?scp=84857092798&partnerID=8YFLogxK

U2 - 10.1002/rcm.6128

DO - 10.1002/rcm.6128

M3 - Article

AN - SCOPUS:84857092798

VL - 26

SP - 583

EP - 591

JO - Rapid Communications in Mass Spectrometry

JF - Rapid Communications in Mass Spectrometry

SN - 0951-4198

IS - 6

ER -