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New Data and a Revised Structural Model for Ferrihydrite

Published online by Cambridge University Press:  02 April 2024

Richard A. Eggleton  and
Robert W. Fitzpatrick
Richard A. Eggleton
Affiliation:
Geology Department, Australian National University, GPO Box 4, Canberra, ACT 2601, Australia
Robert W. Fitzpatrick
Affiliation:
CSIRO, Division of Soils, Glen Osmond, South Australia 5064, Australia
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Abstract

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Synthetic 2-line and 6-line ferrihydrite samples prepared from ferric nitrate solutions have the bulk compositions Fe4(O,OH,H2O)12 and Fe4,6(O,OH,H2O)12, respectively. The composition depends on crystal size, which averages 20 Å for 2-line and 35 Å for 6-line ferrihydrite. X-ray absorption edge spectra indicate the presence of tetrahedral Fe3+, a conclusion supported by heating experiments which show the development of maghemite after heating to 300°C in the presence of N2, followed by the formation of hematite at higher temperatures. These two reactions are recorded on differential thermal analysis traces by exotherms at 350° and 450°C. Transmission electron microscopy shows that 2-line ferrihydrite has no Z-axis regularity but does show hexagonal 2.54-Å lattice fringes. Six-line ferrihydrite forms faceted crystals having 9.4-Å c-parameter only detectable in dark field. In bright field, 2.54-Å lattice fringes indicate greater atomic regularity than in 2-line ferrihydrite. Analysis of the X-ray powder diffraction pattern of 6-line ferrihydrite suggests a structure based on double-hexagonal close-packed oxygens, containing 36% Fe in tetrahedral sites. Selective chemical dissolution, surface area measurements, and magnetic susceptibility are consistent with the recorded properties of ferrihydrite.

Keywords

Crystal structureFerrihydriteIronMagnetic susceptibilitySurface areaSynthesisThermal analysisTransmission electron microscopyX-ray absorption edge spectra
Type
Research Article
Information
Clays and Clay Minerals , Volume 36 , Issue 2 , April 1988 , pp. 111 - 124
Copyright
Copyright © 1988, The Clay Minerals Society

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