0000000000138934
AUTHOR
Christian M. Marquardt
X-ray absorption spectroscopic study of trivalent and tetravalent actinides in solution at varying pH values
Abstract We perform X-ray absorption spectroscopy (XAS) investigations to monitor the stabilization of redox sensitive trivalent and tetravalent actinide ions in solution at acidic conditions in a pH range from 0 to 3 after treatment with holding reductants, hydroxylamine hydrochloride (NH2OHHCl) and Rongalite (sodium hydroxymethanesulfinate, CH3NaO3S). X-ray absorption near edge structure (XANES) measurements clearly demonstrate the stability of the actinide species for several hours under the given experimental conditions. Hence, structural parameters can be accurately derived by extended X-ray absorption fine structure (EXAFS) investigations. The coordination structure of oxygen atoms be…
Stabilization of polynuclear plutonium(IV) species by humic acid
Abstract Although the formation of tetravalent plutonium (Pu(IV)) polymers with natural organic matter was previously observed by spectroscopy, there is no quantitative evidence of such reaction in batch experiments. In the present study, Pu(IV) interaction with humic acid (HA) was investigated at pH 1.8, 2.5 and 3, as a function of HA concentration and for Pu total concentration equal to 6 × 10−8 M. The finally measured Pu(IV) concentrations ([Pu(IV)]eq) are below Pu(IV) solubility limit. Pu(IV)–HA interaction can be explained by the complexation of Pu(IV) monomers by HA up to [Pu(IV)]eq ∼ 10−8 M. However, the slope of the log–log Pu(IV)–HA binding isotherm changes from ∼0.7 to ∼3.5 for hi…
Modeling plutonium sorption to kaolinite: Accounting for redox equilibria and the stability of surface species
Abstract Plutonium with its particularly complex redox chemistry may be thermodynamically stable in the states + III to + VI depending on the redox conditions in the environment. Mineral surfaces can also affect Pu redox speciation. Therefore, the interpretation of Pu sorption data becomes particularly challenging, even for simplified laboratory experiments. The present study focuses on Pu sorption to kaolinite. Am(III), Th(IV), Np(V) and U(VI) literature sorption data are used as analogues for the corresponding Pu redox states to calibrate a simple surface complexation model, and the Nernst formalism is applied. Two independent pH–pe diagrams, one for the kaolinite surface and another for …
Separation of plutonium and neptunium species by capillary electrophoresis-inductively coupled plasma-mass spectrometry and application to natural groundwater samples.
Capillary electrophoresis (CE) was coupled to ICPMS in order to combine the good performance of this separation technique with the high sensitivity of the ICPMS for the analysis of plutonium and neptunium oxidation states. The combination of a fused-silica capillary with a MicroMist AR 30-I-FM02 nebulizer and a Cinnabar small-volume cyclonic spray chamber yielded the best separation results. With this setup, it was possible to separate a model element mixture containing neptunium (NpO2(+)), uranium (UO2(2+)), lanthanum (La3+), and thorium (Th4+) in 1 M acetic acid. The same conditions were also suitable for the separation of various oxidation states of plutonium and neptunium in different a…