TRLFS study on the speciation of uranium in seepage water and pore water of heavy metal contaminated soil

Abstract

In situ leaching of uranium ores with sulfuric acid during active uranium mining activity on the Gessenheap has caused longstanding environmental problems of acid mine drainage and elevated concentrations of uranium. To study there remediation measures the test site Gessenwiese, a recultivated former uranium mining heap near Ronnenburg/East Thuringia/Germany, was installed as a part of a research program of the Friedrich-Schiller University Jena to study, among other techniques, the phytoremediation capacity of native and selected plants towards uranium. In the first step the uranium speciation in surface seepage and soil pore waters from Gessenwiese, ranging in pH from 3.2 to 4.0, were studied by time-resolved laser-induced fluorescence spectroscopy (TRLFS). Both types of water samples showed mono-exponential luminescence decay, indicating the presence of only one major species. The detected emission bands were found at 477.5, 491.8, 513.0, 537.2, 562.3, and 590.7 nm in case of the surface water samples, and were found at 477.2, 493.2, 513.8, 537.0, 562.4, and 590.0 nm in case of the soil water samples. These characteristic peak maxima together with the observed mono-exponential decay indicated that the uranium speciation in the seepage and soil pore waters is dominated by the uranium (VI) sulfate species UO₂SO_4(aq). Due to the presence of luminescence quenchers in the natural water samples the measured luminescence lifetimes of the UO₂SO_4(aq) species of 1.0-2.6 μs were reduced in comparison to pure uranium sulfate solutions, which show a luminescence lifetime of 4.7 μs. These results convincingly show that in the pH range of 3.2-4.0 TRLFS is a suitable and very useful technique to study the uranium speciation in naturally occurring water samples.

Keywords: Pore water; Seepage water; Speciation; TRLFS; Time-resolved laser-induced fluorescence spectroscopy; Uranium (VI).

Fig. 1

Test site Gessenwiese in eastern Thuringia (left), and sample localities within test site. Coordinates are in the German grid (Gauß-Krüger zone 4)

Fig. 2

Time-resolved laser-induced luminescence signal obtained from sample OW2

Fig. 3

Life time curve from the luminescence signal sample OW2

Fig. 4

Intensity from the luminescence signals of the three pore water samples, in comparison with positions of peak maxima published in [13] for UO₂SO_4(aq) (dashed vertical lines)