Mixed-layer clays composed of randomly interstratified kerolite/stevensite occur as lake and/or spring deposits of probable Pliocene and Pleistocene age in the Amargosa Desert of southern Nevada, U.S.A. The percentage of expandable layers of these clays, determined from computer-simulated X-ray diffractograms, ranges from almost 0 to about 80%. This range in expandabilities most likely results from differences in solution chemistry and/or temperature at the time of formation. An average structural formula for the purest clay (sample P-7), a clay with about 70% expandable layers, is:

$${\left[ {\left( {M{g_{2,72}}A{l_{0,07}}F{e_{0.03}}L{i_{0.09}}} \right)\left( {S{i_{3.96}}A{l_{0.04}}} \right){O_{10}}{{\left( {OH} \right)}_2}} \right]^{ - 0.21}}{\left[ {X_{0.21}^ + } \right]^{ + 0.21}}.$$

The data suggest that talc, kerolite, and stevensite form a continuous structural series based on layer charge.

Deposits of sepiolite, trioctahedral smectite (mixed-layer kerolite/stevensite), calcite, and dolomite, found in the Amargosa Flat and Ash Meadows areas of the Amargosa Desert were formed by precipitation from nonsaline solutions. This mode of origin is indicated by crystal growth patterns, by the low Al content for the deposits, and by the absence of volcanoclastic textures. Evidence for low salinity is found in the isotopic compositions for the minerals, in the lack of abundant soluble salts in the deposits, and in the crystal habits of the dolomite. In addition, calculations show that modern spring water in the area can precipitate sepiolite, dolomite, and calcite following only minor evaporative concentration and equilibration with atmospheric CO2. However, precipitation of mixed-layer kerolite/stevensite may require a more saline environment. Mineral precipitation probably occurred during a pluvial period in shallow lakes or swamps fed by spring water from Paleozoic carbonate aquifers.

Ferrihydrite prepared in different manners was kept under relative humidities ranging from 75 to 100% and at temperatures of 45° and 55°C for 180 days. Ferrihydrite transformed to hematite and goethite at relative humidities close to 100%, but at lower relative humidities the transformation was less pronounced and hematite was highly favored over goethite. Increasing temperature also favored hematite over goethite, and Al substitution completely prevented goethite formation. These results suggest that hematite can form in relatively dry, warm soils or sediments, although more slowly than in moister environments.

The effects of exchangeable Na and Ca and the ionic strength of NaCl and CaCl2 solutions on the boron adsorption by the Na and Ca forms of montmorillonite and illite at pH 9 were studied. The boron adsorption by montmorillonite was greater for the Ca form than for the Na form at any boron activity in solution and at any ionic strength. For example, the amount of boron adsorbed by Na- and Ca-montmo-rillonite was 2.9 and 4.3 μmole/g, respectively, at an ionic strength of 0.36 and a boron activity of 0.875 mmole/liter in equilibrium solution. The boron adsorption by illite was much greater than by montmorillonite. For example, the amount of boron adsorbed by Na-montmorillonite and Na-illite was 1.5 and 8.7 μmole/g, respectively, at an ionic strength of 0.02 and a boron activity of 0.5 mmole/liter. However, the nature of the exchangeable cation had little effect on the boron adsorption by illite. The effect of the ionic strength on the boron adsorption by Na-montmorillonite was greater than that observed for either Camontmorillonite or illite. The data suggest that the negative electric field around the clay particles is one of the main factors controlling boron adsorption at alkaline pHs.

The catalytic activity of sepiolite from Amboseli, Tanzania, for the dehydration and dehydrogenation of ethanol at 150°–300°C has been studied using a flow reactor. Both reactions occur, but the catalyst activity decreases with use. The products include water, carbon dioxide, ethene, ethanal (acetaldehyde), diethyl ether, but-1,3-diene, but-2-enal (crotonaldehyde), and an unidentified aromatic compound. The proportions change with temperature, the dehydrogenation reaction being favored at the higher temperatures. The BET surface areas of the sepiolite are 316 m2/g (nitrogen adsorption at — 197°C) and 212 m2/g (ethanol vapor adsorption at 25°C, assuming a molecular cross-sectional area of 24.6 Å2), indicating a possible greater penetration of pores and channels by nitrogen compared with ethanol vapor under these conditions. The pore-size distribution reveals that approximately 55% of the surface area measured by nitrogen adsorption is contributed by micropores.

An iron-rich chlorite, ripidolite, was oxidized by air-heating at 480°C, i.e., below the dehydroxylation temperature and subsequently reduced in hydrogen at the same temperature. On the basis of chemical, differential thermal, infrared, Mössbauer, and X-ray powder diffraction analyses, Fe(II) seems to be present only in the 2:1 layer of the original chlorite in a type of site similar to that of Fe(II) in biotite, with OH in cis-positions. These data also suggest that octahedral Al and Fe(III) are located in the hydroxide sheet of the original chlorite. The structural changes of the mineral due to the oxidation and the subsequent reduction appear limited to minor structural rearrangements and, perhaps, to the introduction of OH in both cis- and trans-positions. The results of the investigation are in agreement with a reaction of the form: [Fe(II)OH]+ ⇋ [Fe(III)O]+ + H(H+ + e−).

From the symmetry point of view, micas may be classified as follows: those with all three octahedrally coordinated sites occupied by the same cation (homo-octahedral micas), those with only two of these sites occupied by the same cation (meso-octahedral micas), and those with the three sites occupied by different cations or by two different cations and a void, in an ordered manner (hetero-octahedral micas). For any of these three classes, mica polytypes, idealized in accordance with the generalized Pauling model, can be interpreted as OD structures consisting of octahedral OD layering and tetrahedral OD layering in which an interlayer cation plane is sandwiched between tetrahedral sheets. A mica layer built up by an octahedral sheet and two halves of tetrahedral sheets on either side consists of two OD packets linked by a two-fold rotation.

The orientation of any OD packet may be given by a number from 0 to 5 (related to a hexagonal coordinate system). A dot behind or before these numbers is used to denote the position of the octahedral layer (number + dot = orientational character). The displacement of a packet against its predecessor is characterized by a vector from the origin of a packet pn (or qn-1) to the origin of the adjacent packet pn+1 (or p2n). These displacements may also be symbolized by numbers from 0 to 5 (displacement characters); a zero displacement is symbolized by *. Any mica polytype (ordered or disordered) can thus be described by a two-line symbol. The orientational characters are located on the first line, and the displacement characters on the second. Any symbol, therefore denotes unequivocally the stacking layers in a polytype. The space-group symmetry of ordered polytypes follows directly from the symbol.

A standardless method of energy dispersive X-ray fluorescence in conjunction with scanning electron microscopy was used to analyze selected areas of clay-size particles of talc, pyrophyllite, and kaolinite supported by a carbon planchet. Peak intensity ratios of fluorescing elements relative to silicon were converted directly to weight or mole ratios using conversion factors determined theoretically. The conversion factors depend upon particle thickness and mass adsorption coefficients of the sample for the elements analyzed. The effects of particle thickness become significant above ~0.1 μm. Without using particle thickness corrections, the mean molar ratios of metal to Si agreed to within 6.1,0.5, and 9.7% of the theoretical ratios for kaolinite, pyrophyllite, and talc, respectively.

An electrostatic model for the stability of clay tactoids (stacks of parallel clay platelets at ~10 Å separation) in an aqueous solution has been developed. The counter ions located in the interstitial water layers are assumed to be in equilibrium with the bulk solution. Generally, the counter-ion charge density is slightly different in magnitude from the platelet charge density. Approximating the discrete charges by homogeneously charged planes, a one-dimensional potential distribution can be calculated. From this the Gibbs energy of electrostatic interaction (using single platelets as a reference) can be computed. The model predicts that clay minerals with high (vermiculite, mica) and low (pyrophyllite, talc) degrees of cationic substitution form stable tactoids. For smectites, charge density, electrolyte concentration, and counterion species determine the swelling characteristics. At a particular charge density, lower valences of the counter ions and lower electrolyte concentrations lead to increased swelling. If tactoids are formed, the number of platelets is governed by a dynamic equilibrium between electrostatic forces, van der Waals forces, and external forces, such as shear forces due to hydrodynamic flow.