The application of UV-Vis and time-resolved laser-induced fluorescence
(TRLF) spectroscopies to direct speciation of uranium(Vr) in environm
ental samples offers various prospects that have, however, serious lim
itations. While UV-Vis spectroscopy is probably not sensitive enough t
o detect uranium(VI) species in the majority of environmental samples,
TRLFS is principially able to speciate uranium(VI) at very low concen
tration levels in the nanomol range. Speciation by TRLFS can be based
on three parameters: excitation spectrum, emission spectrum and lifeti
me of the fluorescence emission process. Due to quenching effects, the
lifetime may not be expected to be as characteristic as, e.g., the em
ission spectrum. Quenching of U(VI) fluorescence by reaction with orga
nic substances, inorganic ions and formation of carbonate radicals is
one important limiting factor in the application of U(VI) fluorescence
spectroscopy. Fundamental photophysical criteria are illustrated usin
g UV-Vis and fluorescence spectra of U(VI) hydrolysis and carbonato sp
ecies as examples.