Cation ordering in amesite-2H2 from Antarctica has reduced the true symmetry from the ideal hexagonal space group P63 to triclinic P1. All crystals show 6-fold biaxial twin sectors on (001), and the twinned crystals produce an average diffraction symmetry that is hexagonal. Individual twin sectors cut from the larger aggregate have 2 V optic angles near 18°, slightly monoclinic unit-cell geometry, and triclinic diffraction symmetry. Structural refinement of an untwinned sector in subgroup symmetry shows nearly complete ordering of Si,Al in tetrahedral sites and of Mg, Al in octahedral sites.

In triclinic symmetry the two layers in the unit cell are no longer equivalent. Tetrahedra lying on the pseudo-63 screw axis are alternately Si-rich and Al-rich in adjacent layers. Of the three octahedral sites in each layer, one is smaller than the other two and is interpreted as Al-rich. The distribution of Al-rich and Mg-rich octahedra violates both the pseudo-3-fold rotation axis within each layer and the pseudo-63 screw axis that relates one layer to the next in the ideal space group. Local charge balance is achieved in adjacent layers by location of all tetrahedral and octahedral Al in lines parallel to X1 and spaced at intervals of b1/2. Similar charge balance patterns parallel to X2 and X3 are postulated to account for the sector twinning, which has been observed also in amesites from Chester, Massachusetts, USA, Saranovskoye, USSR, and Postmasburg, South Africa.

The cation-exchange capacities (CEC) of a previously well-characterized beidellite have been estimated nondestructively from X-ray photoelectron spectroscopy (XPS) data following exchange by various cations. The CEC obtained as an atomic ratio to silicon from Na- and Ca-clays are close to that derived chemically, i.e., 0.10(2), and 0.10(1), respectively, compared with 0.12(1). However, the apparent CEC obtained following K-, Pb-, and Ba-exchange are all about 50% greater. These measurements are complemented by XPS studies of clay exchanged in a solution containing both Ca and Ba ions where XPS gave a total apparent exchange capacity relative to Si of 0.16, with 0.10 from Ca and 0.06 from Ba. Bulk chemical analysis has, however, shown that the true Ba value is only 0.01. It is concluded that the cation excess detected by XPS—a technique with a total sampling depth of only about 100 Å—is concentrated at the surfaces of the clay particles.

Hydrothermal reactions in the system sepiolite/H2O have been examined between 149° and 316°C. Approximately 10–20% of the starting sepiolite was converted to a smectite (stevensite) at 204°C within 24 hr. Similar results were obtained when CaCl2, NaOH, Ca(OH)2, or Mg(OH)2 was added to the system. In the presence of NaCl, about 60% of the sepiolite was converted to stevensite, whereas, only 5% stevensite formed in the presence of MgCl2. Greater amounts of stevensite formed at 260°C in these systems. Above 316°C, 60–80% of the sepiolite was converted to stevensite in 24 hr, regardless of the presence or absence of salts. Within the experimental conditions used, temperature is the most important factor in the sepiolite-to-stevensite conversion.

At or below 216°C, sepiolite appears to transform into stevensite by dislocations involving c12 glides that are triggered by the stresses of the hydrothermal conditions. Above this temperature, stevensite seems to form by direct precipitation after dissolution of sepiolite.

Phosphate in the form of organic compounds can be bound in soils containing the aluminosilicate allophane. A significant part of this phosphorus is believed to be present as nucleic acids. The interaction of yeast RNA with allophane was studied to further the understanding of the allophane/organic macro molecule interaction as well as the binding of organic phosphorus by allophanic soils. The extent of RNA adsorption on the allophane was dependent upon the pH, the charge and concentration of simple cations, the concentration of RNA, and the time of interaction. From a mixture containing 145 mg/liter RNA and 2.9 g/liter allophane in 10−2 M NaCl, the amount of RNA adsorbed increased from 6% at pH 10 to 98% at pH 3. The adsorption also increased as the concentration of added NaCl was increased from 10−4 M to 10−1 M, but only when the pH was greater than 5, i.e., above the isoelectric point of the clay. Mg2+ and Ca2+ were equally much more effective at promoting adsorption than Na+ at the same concentrations. There was no difference in the effectiveness of SO4−2, Cl−, or NO3− at pH 5 or higher. The adsorption isotherm at pH 7 can be described by the Langmuir equation; the apparent adsorption maximum was 38 mg/g. Van der Waals and simple electrostatic forces appear to dominate the interaction leading to the adsorption of RNA by allophane.

The nature of the complexes in aqueous solutions of Cu(II) and Ni(II) with diethylenetriamine (dien) and tetraethylenepentamine tetren) is pH-dependent. At M(II):dien = 2 and M(II):tetren = 1, the main complexes are [M(dien H)2(H2O)2]4+ and [M(tetren H)(H2O)2]3+. In excess ligand (pH = 10.30), the majority species are [M(dien)2]2+ and [M(tetren)(H2O)]2+, and considerable amounts of monoprotonated amines are adsorbed. The surface of hectorite prefers the tetragonally distorted complexes in all cases studied. The complexes readily lose their axially coordinated water molecules to form planar complexes on the interlamellar surface. The planar Ni(II)-complexes are diamagnetic, showing that the surface is a very weak axial ligand. The divalent complexes [M(dien)2]2+ and [M(tetren)(H2O]2+ can also be partially transformed to the corresponding planar forms on the surface, especially in the case of [Cu(dien)2]2+. The driving forces are thought to be the acid nature of the clay-adsorbed water and the gain in crystal field stabilization energy of the transition metal ions.

The adsorption of acetamide and partly hydrolyzed Polyacrylamides onto montmorillonite has been investigated with emphasis on the valency of the exchangeable cation of the clay and the ionic strength of the medium. A difference in the adsorption of acetamide from 3 mg/g to 0.6 mg/g was observed when a Na+-clay was changed to a Al3+-clay. For Polyacrylamide, an opposite effect was observed, and the fixation increased from 3 mg/g (Na+-clay) to 18 mg/g (Al3+-clay). This difference in behavior may be accounted for by the decrease in adsorption sites due to partial flocculation in the presence of polyvalent cations (tactoid formation). Adsorption in a saline medium is two- to fivefold greater for diverse polymers and substantially less for acetamide (from 3.0 mg/g to 0.77 mg/g). An increase in the degree of hydrolysis of the polymer results in a significant increase in adsorption. In contrast, a change of molecular weight has practically no influence upon the adsorption ratio. The results obtained in saline medium may be explained by a size decrease of the macromolecules, allowing a closer approach to the surface of the mineral substrate, and by a chain lengthening as the degree of hydrolysis increases, induced by the electrostatic repulsions between the COO− groups.

Results of adsorption studies of several pesticides on soils and clays show that the application of the reduced concentration concept to adsorption can either reduce the temperature effect on the isotherms, eliminate it altogether (e.g., parathion adsorption on Netanya soil), increase the temperature dependence (e.g., (β-BHC adsorption on Ca-bentonite) or even reverse the temperature dependence of the isotherms (e.g., parathion adsorption on Ca-attapulgite).

Literature and experimental data for the adsorption of parathion by Ca-attapulgite and by attapulgite with organic exchangeable cations of different sizes demonstrate that for many surface interactions the terms organophilic or hydrophilic are misleading. Organic compounds which are insoluble in water and soluble in apolar solvents will not necessarily adsorb preferentially on “organophilic“ surfaces. The specific interactions between adsorbate and adsorbent and steric considerations (in addition to the relative solubility of the organic molecule in water and apolar solvents and the organophilic or hydrophilic nature of the surface) will determine the partition between the adsorbed and the solution phase. An outstanding example is the order of adsorption of parathion on attapulgite: HDMA-attapulgite > Ca-attapulgite > TMA-attapulgite. This order is neither directly nor inversely related to the “organophilic” nature of the surfaces.