K. Dardenne et al., Identification and characterization of sorbed lutetium species on 2-line ferrihydrite by sorption data modeling, TRLFS and EXAFS, RADIOCH ACT, 89(7), 2001, pp. 469-479
The Lu(III) sorbed species onto synthetic hydrous feme oxide (HFO), commonl
y called fenihydrite, has been identified. Characterization of the syntheti
c 2-line HFO shows that its synthesis is reproducible. Potentiometric titra
tion of freshly synthesized HFO, modeled using the constant capacity model
(K-1 = 0.5 F/m(2)) in the FITEQL code, yields a specific surface area S-a o
f 360 +/- 35 m(2)/g (N-2-BET), a site density N-d of 2.86 sites/nm(2) (conc
entration of hydroxyl groups, N-s = 1.71 x 10(-3) mol sites/g HFO), and aci
dity constants pK(a1)(int) = 6.37 and pK(a2)(int) = 9.25. Evaluation of che
mical sorption data reveals the presence of two different Lu surface sorbed
species, dependent on pH; a monodendate species forms at low pH and a poly
dentate species at pH > 5. Satisfactory fits to the sorption data are obtai
ned using a combination of monodentate and bidentate surface species. The c
ombination of species is chosen, based on extended X-ray absorption fine st
ructure (EXAFS) results. The sorption constants obtained from these fits ar
e pK(s) = -1.89(+/-0.1) and pK(s) = -1.69(+/- 0.1) for the monodentate spec
ies drop FeOLu(H2O)(5)(2+) for fits to the pH edge and to the isotherm at p
H 5.9, respectively. A value of pK(s) = 3.69(+/- 0.01) is found for the bid
entate species drop Fe(O)(2)Lu(H2O)(5)(+) for both fits. EXAFS analysis of
sorption samples prepared at 4.5 < pH < 8 shows that Lu is surrounded by a
single first shell of 7 +/- 1 oxygen atoms, at a distance of (2.30 +/- 0.01
) Angstrom in all samples. A second coordination shell of Fe neighboring at
oms at a distance of (3.38 +/- 0.01) Angstrom is observed for sorption samp
les pH greater than or equal to 5.5. This distance is associated with the f
ormation of a bidendate complex with bonding via edge sharing to iron octah
edra. The samples prepared at pH < 5.1 show no Fe shell, as expected for mo
nodentate coordination. No evidence for surface precipitation and no notice
able difference between wet paste and dried powder samples is found.