Bergaya F. Handbook of Clay Science

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References 421

Handbook of Clay Science

Edited by F. Bergaya, B.K.G. Theng and G. Lagaly

Developments in Clay Science, Vol. 1

423

Chapter 8

PROPERTIES AND BEHAVIOUR OF IRON IN CLAY

MINERALS

J.W. STUCKI

Department of Natural Resources and Environmental Sciences, University of Illinois,

W-321 Turner Hall, 1102 S. Goodwin Ave, Urbana, IL 61801-4798, USA

Because iron (Fe) is the fourth most abundant element in the Earth’s crust (6% of

mass), next to oxygen, silicon, and aluminium, its ubiquitous presence in clays and

clay minerals should be no surprise. It is, in fact, an intimate part of many processes

occurring in natural ecosystems. Murad and Fischer (1988) have reviewed many

pools of iron that exist in nature and discussed the geobiochemical cycle of iron

(summarised brieﬂy in Fig. 8.1), illustrating how it is transformed from one pool to

another. They have also pointed out the many connections within and between the

mineral or inorganic phases of iron and its organic or biological phases in the

environment. The number and complexity of these interactions are great, so a com-

plete discussion of the signiﬁcance of terrestrial iron would ﬁll many volumes. In this

chapter, emphasis is placed on a description of the phases in which iron occurs

in clay minerals and the properties and behaviours it imparts to them by virtue of its

susceptibility to oxidation and reduction (redox) reactions. As is evident from

Fig. 8.1, redox is a pathway that is common to several of the inter-pool transfor-

mations and thus exerts much inﬂuence on terrestrial ecosystems.

An expanded treatise on iron in soils and clay minerals was published by Stucki

et al. (1988), who reviewed the chemistry, detection, and characterisation of iron in

oxides, carbonates, sulphides and sulphates, phyllosilicates, agricultural soils, hy-

dromorphic and lateritic soils, and pedogenic process es. The treatise also touched on

the role of microorganisms in determining the fate of iron in soils and sediments.

Since that work was published, much progress has been made in understanding and

characterising structural iron in smectites, especially in relation to redox processes.

Advances have also been made in the study of iron in other phyllosilicate minerals

such as kaolinite an d mica.

The effects of structural iron on clay mineral properties have been reviewed by

Stucki (1988) and Stucki and Lear (1989) . Since then little new information has come

to light regarding the overall effect of structural iron on clay mineral properties,

although much has been learned about the effects brought about by changes in the

DOI: 10.1016/S1572-4352(05)01013-5

oxidation state of iron ( Stucki et al., 2002). The current chapter will focus largely on

the latter aspect.

8.1. PHASES OF IRON IN CLAY MINERALS

Iron-bearing clays are ubiquitous in nature; in fact, the presence of iron in the

structure of smectites is clearly the rule rather than the exception. They may form

through natural or synthetic processes ( Stucki, 1988; Badraoui and Bloom, 1990;

Aoki and Kohyama, 1991; Boiabid et al., 1991; Badaut et al., 1992; Decarreau et al.,

1992; Martin et al., 1992, 1998; Grauby, 1993; Grauby et al., 1993, 1994; Petit et al.,

1995; Giresse and Wiewiora, 2001). Stucki (1988) has illustrated the classiﬁcation

scheme for iron-bearing smectites, for which nontroni te is the dioctahedral end

member. A number of nontronites, varying in total iron contents and some ﬁne

detail of their properties, have been studied (Ko

ster et al., 1999; Gates et al., 2002).

The supply of many of these samples is dwindling, but a new source that is less

limited was recently discovered in Australia (Keeling et al., 2000) and reports of its

characteristics are now beginning to emerge (Frost et al., 2002a, 2002b; Gates et al.,

2002). Montmorillonite also contains struc tural iron, but to an extent of about 3%

by weight compared with about 20% or more for nontronite.

Fig. 8.1. Illustration of some of the forms of Fe that exist in the Earth’s crust and how they

interact. From Murad and Fischer (1988).

Chapter 8: Properties and Behaviour of Iron in Clay Minerals424