es302574j_si_001.pdf (2.47 MB)
Inhibition of Uranium(VI) Sorption on Titanium Dioxide by Surface Iron(III) Species in Ferric Oxide/Titanium Dioxide Systems
journal contribution
posted on 2012-10-16, 00:00 authored by M. Josick Comarmond, Timothy E. Payne, Richard
N. Collins, Gabriel Palmer, Gregory R. Lumpkin, Michael J. AngoveUranium (U(VI)) sorption in systems containing titanium
dioxide
(TiO2) and various Fe(III)-oxide phases was investigated
in the acidic pH range (pH 2.5–6). Studies were conducted with
physical mixtures of TiO2 and ferrihydrite, TiO2 with coprecipitated ferrihydrite, and with systems where Fe(III)
was mostly present as crystalline Fe(III) oxides. The presence of
ferrihydrite resulted in decreased U(VI) sorption relative to the
pure TiO2 systems, particularly below pH 4, an unexpected
result given that the presence of another sorbent would be expected
to increase U(VI) uptake. In mixtures of TiO2 and crystalline
Fe(III) oxide phases, U(VI) sorption was higher than for the analogous
mixtures of TiO2 with ferrihydrite, and was similar to
U(VI) sorption on TiO2 alone. X-ray absorption spectroscopy
of the TiO2 system with freshly precipitated Fe(III) oxides
indicated the presence of an Fe(III) surface phase that inhibits U(VI)
sorptiona reaction whereby Fe(III) precipitates as lepidocrocite
and/or ferrihydrite effectively blocking surface sorption sites on
the underlying TiO2. Competition between dissolved Fe(III)
and U(VI) for sorption sites may also contribute to the observed decrease
in U(VI) sorption. The present study demonstrates the complexity of
sorption in mixed systems, where the oxide phases do not necessarily
behave in an additive manner, and has implications for U(VI) mobility
in natural and impacted environments where Fe(III) (oxyhydr)oxides
are usually assumed to increase the retention of U(VI).