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Incorporation of Al in iron oxyhydroxides: implications for the structure of ferrihydrite

Published online by Cambridge University Press:  09 July 2018

A. Manceau  and
W.P. Gates
A. Manceau*
Affiliation:
ISTerre, CNRS and Université de Grenoble 1, F-38041 Grenoble Cedex 9, France
W.P. Gates
Affiliation:
Department of Civil Engineering, Monash University, Melbourne 3800, Australia
*
*E-mail: alain.manceau@ujf-grenoble.fr
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Abstract

The incomplete miscibility of Al into the ferrihydrite structure has been a recurring issue in understanding the environmental geochemistry of this important oxyhydroxide. During co-precipitation from acidic aqueous solution, ferrihydrite has been observed to accept only up to ∼25 at.% Al without the formation of multi-phasic Al and Fe oxyhydroxides. Using basic chemistry and crystal-chemical relationships we propose here that the saturation limit of Al substitution in the structure of Fe oxyhydroxides is controlled by Al – Al avoidance in a manner that conforms to Pauling's distortion rule. Employing this hypothesis, we show that the predicted miscibility limit for Al incorporation is 25 at.% in ferrihydrite and 33 at.% in goethite, in agreement with previous observations. These results indicate that the classical f-phase model for ferrihydrite best represents observations. Incorrect assignment of Fe site occupancy and other shortcomings of the akdalaite/tohdite model for ferrihydrite are also discussed.

Keywords

ferrihydritestructurePDFHEXSLinus Pauling
Type
Research Article
Information
Clay Minerals , Volume 48 , Issue 3 , June 2013 , pp. 481 - 489
Copyright
Copyright © The Mineralogical Society of Great Britain and Ireland 2013

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