Fougerite is today recognized as a new iron oxide which occurs in waterlogged soils. Fougerite forms as easily as GRs, controls Fe in solution, and has particular properties quite different from the other iron oxides. In addition, Mg enters the mineral.
In soils, the following scheme has been proposed: at the end of dry season, the soil profile is completely oxidized and Fe present in oxides such as goethite or lepidocrocite. When reducing conditions appear, such as in autumn in temperate climate or during the wet season in tropical climate,
FeIII/Fetotal
1 2/3
Ferrihydrite
Goethite Hematite
Maghemite
Magnetite Lepidocrocite
1/3
1/4 1/2
O/O + OH
3/4 1
Fougerite
Fe2+
in solution
Figure 20 Pathways of formation of iron oxides, and role of fougerite and ferrihydrite as reaction intermediates.
280 Fabienne Trolard and Guilhem Bourrie´
with both a supply of organic matter and water saturation, Fe oxides are partly reduced and Fe2þis released in solution. When oxygen enters the soil due to fluctuations in the water table or supply by rain, Fe2þis oxidized and fougerite forms, by co-precipitation of Fe3þwith Fe2þand Mg2þ.
Bacterial activity is strongly suspected as responsible for the formation of this mineral as was observed in laboratory experimentation. Later, with alternate moderately reducing or strongly reducing conditions, thexmole ratio fluctuates, and fougerite is subject to mineralogical transformations, which can be monitored by in situ Mo¨ssbauer spectroscopy (Feder et al., 2005). Oxidation of fougerite at constant Mg mole ratio leads to an increase in the electrical charge of the layer. This can be simply compensated by a deprotonation of water molecules in the interlayer, or OH ions into O2 ions in the hydroxide sheets, or various anions depending on the environmental conditions.
Fougerite acts as a transient phase from Fe2þ of the soil solution to Fe oxides and oxyhydroxides andFig. 20summarizes from literature and our observations the pathways between Fe2þ and iron oxides implying GRs.
Fougerite is a well-crystallized mineral, with a definite structure, stable in its narrow conditions of stability. As it is labile, it transforms easily in other, more stable, iron oxides as soon as conditions become oxidizing. It acts as an intermediate toward oxidation of dissolved Fe2þ, and it also plays a role in the magnesium cycle, and interacts with many other biogeochemical cycles. More generally, fougerite, as other layered double hydroxides (Sparks, 2001), may play an essential role in the formation of clay minerals, both phyllosilicates and iron hydroxides and oxides, and in the control of both major elements (Mg, Fe) and trace metals (Co, Cr, Mn, Ni, and Zn) in the environment.
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