Adsorption of Uranyl on Gibbsite: A Time-Resolved Laser-Induced Fluorescence Spectroscopy Study

Authors

Hyun-Shik Chang, University of WashingtonFollow
Gregory Korshin, University of Washington
Zheming Wang, Pacific Northwest National LaboratoryFollow
John M. Zachara, Pacific Northwest National LaboratoryFollow

Date of this Version

2006

Citation

Environ. Sci. Technol. 2006, 40, 1244-1249

Abstract

Uranyl adsorbed on gibbsite at pH 4.0-8.0 and ionic strengths (ISs) 0.001-0.4 M (NaClO₄) in the absence of carbonate was studied using time-resolved laser-induced fluorescence spectroscopy (TRLIFS) under cryogenic conditions. TRLIFS data showed the presence of several distinct emission components. Their contributions were determined using the evolving factor analysis approach. Four components denoted as species A, B, C, and D were discerned. Each of them was characterized by a characteristic response to pH and IS changes and also by a unique combination of the values of the fundamental transition energyE_0,0, vibronic spacing ∆E, and half-width of the vibronic lines ∆W. Species A and B were major contributors to the overall emission. They were mainly affected by the pH and predominated below and above pH 5.0, respectively. In contrast with that, the contribution of species C was noticeable only at IS ) 0.001 M, while it was suppressed or absent at high IS values. It was concluded that species A and B are likely to correspond to inner-sphere surface aluminol complexes ≡AIOs(UO₂)⁺ and ≡ AIO -(UO₂)OH°, while species C was hypothesized to correspond to electrostatically bound uranyl complexes (predominantly [UO₂(OH)₃]^-).