Multilinear analysis of Time-Resolved Laser-Induced Fluorescence Spectra of U(VI) containing natural water samples

Natural waters' uranium level monitoring is of great importance for health and environmental protection. One possible detection method is the Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS), which offers the possibility to distinguish different uranium species. The analytical identification of aqueous uranium species in natural water samples is of distinct importance since individual species differ significantly in sorption properties and mobility in the environment. Samples originate from former uranium mine sites and have been provided by Wismut GmbH, Germany. They have been characterized by total elemental concentrations and TRLFS spectra. Uranium in the samples is supposed to be in form of uranyl(VI) complexes mostly with carbonate (CO32-)and bicarbonate (HCO3-) and to lesser extend with sulphate (SO42-), arsenate (AsO43-), hydroxo (OH-), nitrate (NO3-) and other ligands. Presence of alkaline earth metal dications (M = Ca2+, Mg2+, Sr2+) will cause most of uranyl to prefer ternary complex species, e.g. Mn(UO2)(CO3) 3(2n-4) (n.{1; 2}). From species quenching the luminescence, Cl- and Fe2+ should be mentioned. Measurement has been done under cryogenic conditions to increase the luminescence signal. Data analysis has been based on Singular Value Decomposition and monoexponential fit of corresponding loadings (for separate TRLFS spectra, the "Factor analysis of Time Series" (FATS) method) and Parallel Factor Analysis (PARAFAC, all data analysed simultaneously). From individual component spectra, excitation energies T-00, uranyl symmetric mode vibrational frequencies omega gs and excitation driven U-Oyl bond elongation. Delta R have been determined and compared with quasirelativistic (TD) DFT/B3LYP theoretical predictions to cross-check experimental data interpretation.