Laser Induced Spectroscopy - Detection of Species at Low Concentrations

Especially in Saxony and Thuringia the intense uranium mining and milling causes a wide variety of contaminated waters. These seepage and mine waters contain besides uranium several inorganic and organic complex forming agents [1, 2].
Heavy metals in the aquatic environment are normally transported as a complexed species. Knowledge about the complex formation is therefore an essential constituent in prediction of the migration of these elements.
Spectroscopic methods have the advantage to be non-invasive and non-destructive. The high intensity of laser light sources allows the excitation of all species in the illuminated volume. Therefore laser based methods reach low detection limits.
At higher concentrations uranium forms often poly-nuclear complexes. Therefore studies of the complex formation should be carried out at concentrations which are relevant to those of the contaminated sites. Also the direct determination of the species formed in the mining related waters is essential for the selection of effective cleaning methods.
As uranium(VI) shows fluorescence properties (except carbonate species) time-resolved laser-induced fluorescence spectroscopy enables the detection of species up to detection limits of 10-8 M. Besides the study of the complex formation (sulfate, phosphate, arsenate) we determined the formed species in several mining related waters as function of pH. The change in the speciation of uranium(VI) is shown to be in agreement with calculations, if also the formation of formerly unknown species is included.
Carbonate species are dominating the uranium(VI) speciation in the neutral pH range. As mentioned above these species do not emit fluorescence. Uranium(IV) does not show fluorescence properties. In these cases only the absorption spectra can be used for the direct determination of these species. However the concentration of uranium in the natural environment is much lower than the detection limit of conventional UV-VIS spectroscopy. Using laser-induced photoacoustic spectroscopy the detection limit can be decreased by about three orders of magnitude. Studies of the complex formation of uranium(IV) with phosphate and arsenate will be presented [3], demonstrating the advantage of direct speciation methods.

[1] G. Geipel, G. Bernhard, M. Rutsch, V. Brendler, H. Nitsche; Speciation in Water Released from Mining and Milling Facilities In T.E. Baca and T. Florkowski (eds.), The environmental Challenges of Nuclear Disarmament, Kluwer Academic Publishers, 2000, p. 323-332
[2] G. Bernhard, G. Geipel, V. Brendler, H. Nitsche; Speciation of Uranium in Seepage Waters from a Mine Tailing Pile Studied by Time-Resolved Laser-Induced Fluorescence Spectroscopy (TRLFS); Radiochimica Acta, 74, 87, (1996)