The 57Fe Mössbauer spectra of six nontronite samples were measured at appropriate temperatures of 4.2 and 1.3 K. Three of the nontronites gave a complex magnetic hyperfine spectrum showing magnetic ordering at 4.2 K, and the other three required a lower temperature of 1.3 K to produce similar magnetic ordering. The spectra were computer-fitted with three closely overlapping sextets which are considered to arise from: (1) Fe3+ that is ordered magnetically in the cis-octahedral sites with a greater number of neighboring tetrahedral Fe3+ ions (51 T); (2) the cis-octahedral site with the greater number of neighboring Si4+ ions (46 T); and (4) the tetrahedral sites (41 T). In an untreated sample a further sextet corresponding to interlayer Fe3+ (36 T) was identified. The magnetic ordering was complicated and not directly related to the iron content of these sites. It probably depended also on the overall composition and structural order of the particular nontronite. The ordering appears to have been essentially two-dimensional, consistent with the layer structure of this material.

Crystal growth theory was applied to describe edge sites of phyllosilicates. Three face configurations were found to exist. One face has one tetrahedral site per tetrahedral sheet and two octahedral one-coordinated sites per crystallographic area ac sin β, where a and c are layer dimensions and β is the angle between them. The other two faces are similar except that they have one less octahedral site which is replaced by one SiIV-O-AlVI site in this same ac sin β area. A transfer of bonding energy from the remaining octahedral site to the SiIV-O-AlVI site is believed to neutralize all edge charge on faces containing these latter sites at normally encountered pHs (pH 3–9). A similar charge rearrangement along the edges results in an apparent decrease in the permanent charge of the mineral with an increase in edge area.

On the basis of such an analysis, lath-shaped illite can be described as a very fine grained dioctahedral mica in which the apparent deficient occupancy of the octahedral sheet, presence of excess water, and measurable cation-exchange capacity may in part be the result of a large ratio of edge area to total volume, with no other chemical or structural change in the mica layers. The increasing importance of edge charge relative to layer charge produces erroneous formulae for 2:1 phyllosilicates in very fine grained samples containing fewer than 2 of 3 octahedral sites occupied by cations, on the basis of a 22-charge half cell.

The 57Fe Mössbauer spectra of untreated, Ca- and K-saturated nontronite from Garfield, Washington, were measured. The spectrum of the untreated sample was computer-fitted to 8 peaks defining two octahedral, a tetrahedral, and an interlayer Fe3+-quadrupole-split doublets. In the Ca- and K-saturated samples interlayer Fe was absent. Spectra of the untreated sample were recorded at increasing increments of background counts from 2.8 × 105 to 9.2 × 106. An evaluation of the initial 4- and 6-peak models and the acceptable 8-peak model, computer-fitted to each spectrum, shows that if the χ2 value is used as a measure of the goodness of the fit, the spectra should be recorded to a background count greater than 3 × 106. The resulting χ2 value then reflects both the validity of the model used and the extent of disorder within the structure. The χ2 value depends linearly on the background counts obtained.

A comparison of the spectra of the Ca- and K-saturated samples with that of the untreated sample shows that the interlayer cations exert a considerable influence on the individual component resonances, particularly the outer octahedral doublet. Hence, it is likely that electrostatic interactions of the nearby tetrahedral Fe3+ and the interlayer cations give rise to two distinct electric field gradients within neighboring cis-[FeO4(OH)2] sites, and hence two octahedral Fe3+ doublets in the Mössbauer spectrum. These results are consistent with earlier electron diffraction data in the literature.