title: Interaction of Fe(III) and Al(III) during hydroxylation by forced hydrolysis: the nature of Al-Fe oxyhydroxy co-precipitates.
abstract: Al-Fe oxyhydroxy co-precipitates were synthesised by forced hydrolysis of Fe(NO3)3·9H2O and Al(NO3)3·9H2O solutions. Solids containing 0, 1, 10, 25, 50, 75, 90 mol% Al were characterised for composition, texture, mineral structure and local atomic environment. Cation substitution in the hydrous oxides was not observed. The solids consisted of hydrous ferric oxide (HFO) nuclei surrounded by Al-hydroxide. Below 50 mol% Al, unit particle size, high specific surface area and microporosity of HFO were preserved. Al-K-edge XANES showed ordered arrangements of Al-octahedra suggesting that some Al bound specifically to HFO surface sites. Above 50 mol%, Al precipitated in multiple layers around the nuclei and also as individual entities. The HFO nuclei exhibited the general characteristics of a 2-line ferrihydrite. However, as Al increased, the structure was slightly modified. While the symmetry of the FeO6 octahedra improved, the number of Fe-Fe linkages decreased, suggesting less polymerisation. An organisation of the Fe-octahedra, faintly resembling akaganeite, was expressed in Raman spectra. These changes in HFO structure were attributed to hindrance in the progressive olation/oxolation of the primary Fe-hydroxypolymers, caused by Al bound to the surface of nuclei. The presence of nitrate is suspected to have favoured the structural changes.
authors.affiliation: Géosystèmes, UMR 8217 CNRS, Department of Earth Sciences, Université Lille 1, 59655 Villeneuve d'Ascq, France. annette.hofmann@univ-lille1.fr
authors.forename: Annette
authors.initials: A
authors.lastname: Hofmann
authors.forename: Delphine
authors.initials: D
authors.lastname: Vantelon
authors.forename: Emmanuelle
authors.initials: E
authors.lastname: Montargès-Pelletier
authors.forename: Françoise
authors.initials: F
authors.lastname: Villain
authors.forename: Olivier
authors.initials: O
authors.lastname: Gardoll
authors.forename: Angelina
authors.initials: A
authors.lastname: Razafitianamaharavo
authors.forename: Jaafar
authors.initials: J
authors.lastname: Ghanbaja
keywords: Akaganeite; Al sorption; Al/Fe-oxyhydroxide; Co-precipitation; Core-rim structure; Forced hydrolysis; HAO; HFO; Nitrate-content