Mössbauer spectra of 15 hematites with Al substitutions between 0 and 10 mole % were taken at room temperature. X-ray powder diffraction indicated dimensions of these hematites in the c-direction to range upwards from 27 nm to crystals large enough to show no line broadening. The Mössbauer spectra showed that magnetic hyperfine fields decreased both with increasing Al-for-Fe substitution and with decreasing crystal size. These relationships indicate that hyperfine field variations cannot, as has been done in the past, be unequivocally related to Al substitution alone. Hyperfine field reductions were paralleled by Mössbauer line broadening due to hyperfine field distributions. Only the hematites heated to 1000°C showed a significant variation of quadrupole splittings with Al substitution. No dependence of quadrupole splitting on crystal size was observed, indicating no detectable distortion of coordination polyhedra in the particle size range studied.

Regularly interstratified chlorite/smectite (corrensite) occurs as grain coatings in marine and eolian sandstones of the Permian Cutler Formation in Lisbon Valley, Utah. Corrensite dominates the <2-μm clay size fraction along with lesser amounts of regularly interstratified illite/smectite in bleached, permeable sandstones that are interbedded with smectite-dominated arkosic, red, laterally discontinuous fluvial sandstones. Chemical and X-ray powder diffraction analyses of the corrensites show them to be di/dioctahedral with 060 spacings of 1.501 to 1.508 Å and to contain significantly higher Al:Mg ratios than more common trioctahedral types. Calculated structural formulae are: corrensite, M0.6(Fe3+0.2Mg1.6Al4.6)(Al0.2Si7.8)O20(OH)10; illite/smectite, M1.5(Fe3+0.1Mg1.7Al2.8)(Al1.6Si6.4)O20(OH)4; and smectite, M0.9(Fe3+0.3Mg1.2Al2.8)(Al0.6Si7.4)O20(OH)4.

Chemical similarity between the smectite and the corrensite and pervasive distribution of smectite in low-permeability shales and siltstones suggest that the smectite was a precursor of the corrensite. Three stages of mineral precipitation in the Cutler Formation have been recognized. Quartz precipitated early as grain overgrowths, followed by the formation of authigenic clay minerals, and later calcite cementation which destroyed much of the original rock fabric. Calculations show that aluminous corrensite was favored by elevated temperature (∼ 100°C), low pH, and low dissolved silica. Local hydrothermal fluids rising along the Lisbon fault apparently permeated the Cutler red bed section and precipitated the clay minerals. The assemblage corrensite + illite/smectite in the sandstones probably formed by interaction of formation fluids with smectite and an Al-bearing phase, such as K-feldspar or kaolinite.

The southern San Joaquin Valley contains more than 7 km of sedimentary fill, largely Miocene and younger in age. Ancient depositional environments ranged from alluvial fans at the basin margins to turbidite fans toward the basin center. Mixed-layer illite/smectite (I/S) dominates the <2-μm fraction of Miocene shales, and kaolinite is abundant in Miocene sandstones. I/S from carbonate-cemented sandstones contains 5–20% more smectite layers than I/S from uncemented sandstones. The timing of cementation correlates with the proportion of smectite layers in the I/S, suggesting that cementation slowed the illitization process. Smectite and I/S with > 80% expandable layers occur at present burial temperatures of 120°-l 40°C in Miocene sandstones and shales. This highly expandable I/S is restricted to areas covered by thick deposits (1000-2500 m) of Pleistocene sediments. Rocks of similar age and at equivalent temperatures, but covered by <900 m of Pleistocene sediments, contain I/S having low expandabilities (<30%).

Microprobe analyses of 16 discrete smectite and smectite-rich I/S clays indicate an average montmorillonite composition of:

$$\left( {C{a_{0.2}}{K_{0.15}}N{a_{0.1}}} \right)\left( {A{l_{3.0}}F{e^{3 + }}_{0.35}M{g_{0.75}}T{i_{0.03}}} \right)\left( {S{i_{7.7}}A{l_{0.3}}} \right){O_{20}}{\left( {OH} \right)_4} \cdot n{H_2}O.$$

Residence time at different temperatures appears to be an important influence on the percentage of smectite layers in I/S from the San Joaquin basin. Areas containing I/S with high expandabilities (e.g., 95% smectite layers) have a time-temperature index (TTI) of 4.0-4.5 at 120°C, whereas areas containing I/S with low expandabilities (e.g., 30% smectite layers) have a TTI of 5.0. Present data suggest that highly expandable I/S changed to slightly expandable I/S over a narrow temperature interval (10°-20°C). Differences in the potassium availability from detrital components and in the K+/H+ activity ratios of pore water do not appear to be related to the differences in the percentage of smectite layers of these I/S clays.

Nine hematites and 22 goethites were synthesized by a variety of methods to obtain monomineralic samples having a range of Al substitutions and particle sizes. The second derivative of absorbance and Munsell color designations were calculated from visible reflectance spectra obtained from the dry powders. Unit-cell dimensions, Al substitution, infrared band positions, mean crystallite dimensions (MCD) from X-ray powder diffraction, and particle size from fiber-optic Doppler anemometry (FODA) were determined. Previously reported correlations between Al substitution, goethite unit-cell dimensions, and OH-stretching and -bending band positions were confirmed. For hematite, the position of the second derivative peak at ∼600 nm was negatively correlated with Al substitution (r = −.86). Munsell value and chroma were positively correlated with Al substitution (r =.94 for both), but hue was not related to Al substitution. Hue appeared to become redder, however, as particle size measured either by FODA or MCD increased. For goethite, the position of the second derivative minimum at ∼485 nm was negatively correlated with Al substitution (r = −.99). Munsell hue appeared to be related to both Al substitution and MCD perpendicular to (110), MCD110, with hues becoming redder with increasing Al substitution and yellower with increasing MCD110. Correlations between Munsell value and chroma and parameters such as Al substitution, particle size, and OH-stretching and -bending band positions were poor, but goethites synthesized by oxidation of Fe2+ solutions at room temperature had higher chromas than goethites synthesized hydrothermally from an Fe3+ system. Visually determined colors agreed well with calculated ones. Second-derivative spectra and color designations calculated from visible spectra appear to be potentially useful for quickly estimating other properties of goethite and hematite, such as Al substitution and particle size.

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.

The crystal structures of a reddish-purple, Mn-bearing muscovite-2M1 (alurgite variety) and a reddish-brown, Mn-bearing phlogopite-1M (manganophyllite variety) were refined to final residuals of 2.7% and 3.1%, respectively. The refinements were carried out in space groups C2/c and C1 for alurgite and C2/m and C2 for manganophyllite. The C1 and C2 subgroup refinements gave atomic coordinates consistent with the parent space group refinements. No cation ordering was found in either specimen, and the structures are very similar to those of muscovite and phlogopite. Residual areas of positive electron densities were found between the tetrahedral cations and neighboring oxygens in difference maps of both minerals. Those of alurgite were examined in detail to show the correlation between the residual densities and covalent bonding in the tetrahedra. The valence of the Fe present was determined by Mössbauer spectra as Fe3+ in both samples and of the Mn by optical spectra as Mn3+ in the alurgite but as Mn2+ in the manganophyllite.

Hydrotalcite-like compounds, [Mg1-xAlx(OH)2]x+ [xX−·n H2O], where X− = ½CO32− or OH−, were prepared by hydrothermal syntheses at $P_{H{}_{2}O}=100MPa$ and T = 100°–350°C. Starting materials were MgO, γ-Al2O3, H2O, and MgC2O4·2H2O. The synthesis depended on temperature, pressure, the Al/(Al + Mg) ratio x, and the CO2 content of the starting material. Previously an Al content of x = 0.33 was thought to be the upper limit in these double-layer compounds, but by using pressure the Al-content was increased to x = 0.44. Up to x = 0.33, a0 decreased linearly to about 3.04 Å, but for x ≥0.33, a0 remained nearly constant at this value. For the synthesized products the layer thickness c’ varied between 7.40 and 7.57 Å in contrast to the natural phases wherein c’ varies from 7.60 to 7.80 Å. At higher temperatures CO2-free syntheses, i.e., those without Mg-oxalate, resulted in a disordered hydrotalcite-like phase. The transition temperature between the ordered and the disordered hydrotalcite-like phase depended on the Al-content, x.

A closed-form equation was derived that describes the powder-ring distribution factor as a function of 2θ, soller slit collimation, and σ*, which is defined as the standard deviation of an axially symmetrical Gaussian orientation function. Methods were developed for measuring σ* in the reflection mode by means of a θ/2θ diffractometer. Six experimental arrangements for a sedimentary chlorite showed widely different intensity ratios of the 001/005 reflections and gave a standard deviation of ±5.8% when corrected by the theory. The absolute integrated intensities of the 003 reflection from eleven illite samples provided an eight-fold maximum range which, when corrected, yielded a standard deviation of ±7.7%.

The intensity distributions within each of two X-ray powder diffraction patterns obtained from instruments with different soller-slit configurations could not be directly compared at low diffraction angles unless corrections, based on σ*, were introduced to allow for the differences in axial divergence.

Intercalates of Georgia well-crystallized kaolinite with formamide, N-methylformamide (NMF), and dimethylsulfoxide (DMSO) were prepared at room temperature by dispersing the clay in the organic liquid. Several physical and chemical properties of the intercalated organic molecules and the clay, while intercalated and after de-intercalation, were examined using nuclear magnetic resonance (NMR), infrared (IR), and electron paramagnetic resonance spectroscopy (EPR), and specific heat (Cp) measurements. The chemical bonding between the inner-surface hydroxyls and the organic molecules, as indicated by IR, was strongest for DMSO and weakest for formamide. The distortion of the kaolinite layer, as shown by EPR, also was greatest for DMSO and least for formamide. NMR T1 measurements indicated a relatively strong DMSO-kaolinite surface interaction that slowed down the methyl group reorientation comparable to that in bulk solid DMSO. T1 measurements indicated a weaker interaction for NMF. De-intercalation by mild heating did not return the kaolinite to its original structural state as shown by EPR and Cp. The greatest disorder was found for the DMSO de-intercalate and the least for the formamide de-intercalate. These experiments show that for sufficiently strong bonding between the clay inner surface and the intercalating molecule, the structure of the clay is capable of distortion, which is partly temporary and partly permanent. The permanent changes probably involve the introduction of stacking faults.

The effect of heating synthetic microcrystalline goethite at 60°, 80°, and 105°C was studied by X-ray powder diffraction, electron microscopy, weight-loss measurements, and Mössbauer spectroscopy. Heating led to no detectable changes in the unit-cell parameters or crystallite size (210, 150, and 170 Å in the [020], [110], and [120] directions, respectively), however, some of the X-ray diffraction lines were broadened due to an increase in microstrain in these crystallographic directions. The superferromagnetic transition temperature increased from 43° to 46°, 53°, and 54°C after heating to 60°, 80°, and 105°C, respectively, showing that the desorption of water from the surfaces led to an enhanced magnetic coupling among the crystallites.

Chemical data from three different series of diagenetic illite/smectites (I/S), analyzed statistically by two regresion techniques, indicate that the content of fixed-K per illite layer is not constant, but ranges from ~0.55 per O10(OH)2 for illite layers in randomly interstratified I/S (R=0; >50% smectite layers) to ~ 1.0 per O10(OH)2 for illite layers formed in ordered I/S (R>0; <50% smectite layers). By extrapolation of the experimental data, the following chemical characteristics were obtained for end-member illite derived from the alteration of smectite in bentonite: average fixed-K per illite layer = 0.75 per O10(OH)2; total charge = about -0.8; cation-exchange capacity = 15 meq/100 g; surface area (EGME) = 150 m2/g.

Junction probability diagrams show variation in both composition and layer arrangement in mixed-layer clay minerals. These diagrams can represent short-range and long-range ordered, random, and segregated interstratifications. Mineralogical analyses of illite/smectite from shale cuttings, bentonites, and hydrothermally altered tuffs define characteristic reaction pathways through these diagrams. Shale and bentonite analyses fall along pathways joining smectite and illite on diagrams showing nearest-neighbor (R1) layer arrangements. Transition from random to R1-ordered interstratifications occurs in shale samples containing 60–70% illite layers, and in bentonites containing 55–67% illite layers. Analyses of alteration products, however, fall near a line connecting rectorite and illite, which represents the maximum degree of R1 layer ordering. No mineralogical evidence is available to suggest that these alteration samples formed from a smectite precursor. All samples develop next-nearest (R2) and thrice-removed (R3) neighbor ordering along similar pathways. Transition to R2 ordering occurs gradually in samples composed of 65–80% illite layers, and samples containing more than 85% illite layers may show strong R3 ordering.

A suite of Georgia kaolinites, ranging from well-ordered to very poorly ordered samples, were studied to explore correlations between degree of structural disorder, geological environment, Fe3+ content, Fe3+ electron paramagnetic resonance (EPR) spectrum, and infrared (IR) hydroxyl-stretching band frequencies and bandwidths. Samples from different localities showed a wide range of disorder which appears to be related to differences in their geological environments. High iron content correlated strongly with low degree of order. The areas of both the I and E components of the EPR spectrum and the fractional I area correlated inversely with degree of order. Fourier-transform IR studies of kaolinites and dickites showed that (1) interlayer hydrogen bonding is weaker in dickite than in kaolinite; (2) frequency of the ν11 stretching band of the inner-surface hydroxyls increases sequentially from well-ordered kaolinite through the disordered structures to well-ordered dickite, which is consistent with a model for disorder based on vacancy displacement; and (3) the character and temperature dependence of the inner hydroxyl-stretching band is not compatible with the crystal structures of kaolinite and dickite as refined by Suitch and Young.

Synthetic sodium bimessite, having a cation-exchange capacity (CEC) of 240 meq/100 g (cmol/kg) was transformed into Li, K, Mg, Ca, Sr, Ni, and Mn2+ cationic forms by ion exchange in an aqueous medium. Competitive adsorption studies of Ni and Ba vs. Mg showed a strong preference for Ni and Ba by bimessite. The product of Mg2+-exchange was buserite, which showed a basal spacing of 9.6 Å (22°C, relative humidity (RH) = 54%), which on drying at 105°C under vacuum collapsed to 7 Å. Of the cation- saturated bimessites with 7-Å basal spacing, only Li-, Na-, Mg-, and Ca-bimessites showed cation exchange.

Heating bimessite saturated with cations other than K produced a disordered phase between 200° and 400°C, which transformed to well-crystallized phases at 600°C. K-exchanged bimessite did not transform to a disordered phase; rather a topotactic transformation to cryptomelane was observed. Generally the larger cations, K, Ba, and Sr, gave rise to hollandite-type structures. Mn- and Ni-bimessite transformed to bixbyite-type products, and Mg-bimessite (buserite) transformed to a hausmannite-type product. Li-bimessite transformed to cryptomelane and at higher temperature converted to hausmannite. The hollandite-type products retained the morphology of the parent bimessite. The mineralogy of final products were controlled by the saturating cation. Products obtained by heating natural bimessite were similar to those obtained by heating bimessite saturated with transition elements.

The 001 spacing of Na-smectite was found to vary from 9.6 Å at 0% relative humidity (RH) to 12.4 Å at 60-65% RH. The 9.6-Å spacing corresponds to dehydrated Na-smectite, and the 12.4-Å corresponds to Na-smectite with one water layer. A regular series of intermediate values resulted from ordered interstratification of the 9.6- and 12.4-Å units. Ordered interstratification was confirmed by the presence of a 001 spacing of 9.6 + 12.4 Å = 22 Å. This peak appeared under experimental conditions at about 35% RH. It appeared for calculated simulations of ordered stacking of 50/50 mixtures (±10%) of 9.6- and 12.4-Å units. The 004 peak of this 22-Å spacing interacted with the 002 of the 9.6-Å spacing of ordered mixtures of more than 50% 9.6-Å units and with the 002 of the 12.4-Å spacing of ordered mixtures of more than 50% 12.4-Å units. The result of this interaction was a complex peak, the position of which was a function of the ratio of 9.6- and 12.4-Å units. This complex peak was noted for experimental and for calculated conditions. Calculated tracings assuming ordered stacking matched the experimental tracings closely, whereas those assuming random stacking did not.

Ordering was apparently due to the interaction of the positive charge of the interlayer cation repelling the positive charge of the hydrogens of the hydroxyl ions, one above and one below, closest to the interlayer space. The collapse of a single interlayer space (dehydration) brought the interlayer cation closer to the hydrogens of the hydroxyls causing the hydroxyls to rotate such that the hydrogens shifted toward the adjacent interlayer spaces. Collapse of these two interlayer spaces was therefore more difficult. This same mechanism helps explain ordering in illite/smectite. The difference is that hydration/dehydration is quick and reversible, whereas the change from smectite to illite is slow and irreversible.

A layer-by-layer mechanism explains important features of mixed-layer clay minerals formed during the illitization of smectite, including the occurrence of randomly interstratified illite/smectite, the transition to ordered interstratifications, and the development of long-range ordering. A variety of solid-state transformation mechanisms were tested with a stochastic model, which accounts for interactions among clay layers. The model produces most successful results when the reaction of smectite layers with one illite nearest neighbor is favored over smectites with no illite neighbors by a factor of about two, and over those with two illite neighbors by a factor of ten or more. Synthetic X-ray powder diffraction patterns calculated from model results compare well with those of illite/smectite minerals. These results suggest a new kinetic rate law. Solutions to this rate law for reaction within sediments undergoing burial give mineralogical profiles with depth similar to those observed in subsiding sedimentary basins.