Thin clay films prepared from aqueous suspensions of the potassium or sodium salt of picloram (4-amino-3,5,6-trichloropicolinic acid) with Al-, Fe-, or Cu-saturated montmorillonite or with montmorillonite coated with hydrous oxides of Al, Fe, or Cu were examined in an air-dry condition by infrared (IR) techniques to elucidate possible modes of interaction between picloram and the mineral surfaces. Deuteration was used to confirm band assignments of picloram and its salts prior to interaction with montmorillonite. Picloram interactions with Al- and Fe-saturated montmorillonite and with montmorillonite coated with hydrous oxides of Al and Fe were concentration dependent. At high picloram concentrations similarities with the IR spectrum of potassium picloram indicated that much of the picloram was present in the salt form. As the concentration of picloram was reduced below that equivalent to 1 meq/g clay, the IR spectrum indicated the presence of the monomeric acid on the mineral surface. The spectrum of picloram on montmorillonite with a coating of copper hydrous oxide was similar to that of a Cu-picloram complex indicating coordination type bonding. The spectrum of picloram with Cu-saturated montmorillonite did not correspond to any of the other spectra of picloram examined. The interaction of picloram with montmorillonite coated with a hydrous oxide coating of Cu and with Cu-saturated montmorillonite were independent of picloram concentration in the range 2.20-0.44 meq/g clay.

The clay fraction of an Attic soil has been fired at temperatures up to 1100°C and the transformations induced by firing were studied by Mössbauer spectroscopy. The unfired clay contained iron in the form of small particles of α-Fe2O3 and β-FeOOH and as a substitutional ion in the clay mineral structure. A transformation of β-FeOOH to α-Fe2O3 is observed in the region of 200–400°C followed by dehydroxylation of the clay mineral between 500 and 800°C. A disintegration of the clay mineral structure is inferred above 800°C, followed by recrystallization in an iron-rich phase, most probably in the form of very fine particles. The room temperature spectra of the fired samples indicate that an increase in particle size of the oxides occurs upon firing.

The most prominent authigenic reaction in Holocene tuffaceous sediments at Teels Marsh, Nevada, is the hydration of rhyolitic glass by interstitial brines and the subsequent formation of phillipsite. This reaction has the form: rhyolitic glass + H2O → hydrous alkali alumninosilicate gel → phillipsite. Phillipsite is the most abundant authigenic phase in the tuffaceous sediments (>95%), analcime is the next most abundant phase, and clinoptilolite occurs as a trace mineral in the <2-mm fraction. Analcime forms by the reaction of phillipsite and Na+. Gaylussite and searlesite also are common authigenic phases at Teels Marsh. The concentration of silica in the interstitial brines is controlled by one or more of the authigenic reactions at less than 100 ppm. A stoichiometric equation for the reaction of phillipsite to analcime at Teels Marsh is:

$$0.43N{a + }\, + {K_{0.43}}N{a_{0.57}}AlS{i_{3.1}}{O_{8.2}}\, \cdot \,3.2{H_2}O\, \to \,NaAlS{i_2}{O_6}\, \cdot \,{H_2}O\, + \,1.1{H_4}Si{O_4}\, + \,0.43{K + }.$$

Sodium and potassium activities of brines associated with both phillipsite and analcime were used to estimate the equilibrium constant for this reaction as 3.04 × 10−5. The ΔG0 value for the reaction is +6.2 kcal/mole at 25°C and 1 atm pressure. The estimated ΔG0 value of phillipsite, using this reaction, is −1072.8 kcal/mole at 25°C and 1 atm.

Aluminum interlayers were synthesized under the same experimental conditions in a number of vermiculites and montmorillonites from different sources to determine the effects of the degree of neutralization of Al solutions, the time of reaction, and the type of structure.

Vermiculite fixed Al as well as hydroxy-Al ions in its interlayers, producing a stable 14 Å spacing and decreasing its cation exchange capacity considerably. Heating the Al-interlayered vermiculite at 300°C produced an interstratified mixture, indicating that some interlayers collapsed while others did not. The different collapse was attributed to different charge on vermiculite layers.

Neither the aging of vermiculite in Al solutions nor their OH/A1 ratios changed the stability of the interlayers appreciably.

Montmorillonites, on the other hand, did not fix Al ions but fixed appreciable amounts of hydroxy-Al ions. In addition, the stability of the interlayers in montmorillonite increased on aging in hydroxy-Al solutions and exceeded the stability of the interlayers produced in vermiculite. To explain the greater stability of montmorillonite interlayers, it was postulated that the more expanded interlayer space in montmorillonite provides a favorable locale for the organization of hydroxy-Al ions into gibbsite structure while the restricted expansion in vermiculite prevents it.

Adsorption isotherms for water vapor, c-spacing and heat of immersion in water of mixed Na/Ca-montmorillonite were measured at 25°C at various RH. There was good agreement between the calorimetric data, the heat calculated from the isotherms by use of BET equation, and the calculations from the ion-dipole model. It was concluded that the electrostatic forces between the adsorbed cations and the water molecules are the dominant forces in the hydration of the clay. Thus, at low moisture content, only the adsorbed Ca-ions are hydrated. The heat released when Na-platelets condense to form Ca-packets was measured, and it was suggested that this energy term is the driving force for the demixing phenomena.

Bulk (lump) densities of 31 kaolins were measured on the clay in the natural or raw state after drying at 100°C and after firing to 1510°C (2700°F). The kaolins were selected from such diverse origins as surface-weathered and sedimentary accumulations, hydrothermally altered bodies and flintclay deposits. The sedimentary group ranged in density from 0·82 to 1·85 in the dried raw clay, and 1·93 to 2·63 when fired. The hydrothermally altered clays ranged from 1·83 to 2·50 in the dried raw state, and 2·02 to 2·66 when fired. Flint clays ranged from 2·20 to 2·60 in the dried raw state (a “toasted clay” from Russia, 1.75), and 1·99 to 2·70 when fired. The effect of the genetic process on bulk density values is discussed and related.

The conversion of lepidocrocite (-γFeOOH) to its more stable polymorph, goethite (αFeOOH) was followed by observing changes in crystal morphology, oxalate solubility, surface area and X-ray diffraction. In conjunction, kinetics were measured as functions of surface area, temperature, alkalinity and seeding with goethite crystals.

The results suggest that the transformation is not topochemical, but proceeds through the solution phase. The main steps governing the rate of transformation are, (1) the dissolution of lepidocrocite, and (2) the formation of goethite nuclei and subsequent growth. Either of these processes can be rate-determining under appropriate conditions.

Zinc silicates were synthesized under conditions analogous to surficial weathering environments. The main product, regardless of conditions of precipitation or ageing, was shown by X-ray, i.r., electron microscopic and chemical evidence to be a 2:1 layered zinc silicate equivalent of stevensite. In the presence of aluminium, a 1:1 layered zinc silicate was formed as well, in confirmation of published work. The stability of the zinc silicate, in relation to carbonate, was favoured by the presence of aluminium in the lattice and silicic acid in the equilibrium solution. Zinc layer silicates were formed under conditions that generated orthorhombic zinc hydroxides and/or basic salts in the absence of silicon; the involvement of the brucitic zinc hydroxide (α-form), as proposed by earlier workers, could not be supported. Crystalline zinc layer silicates were formed by the slow evolution of the initial gels. Such layer silicates, but not willemite or hemimorphite, could have an important role in the control of chemical reactions of zinc in soils.

Extinction bend contours, observed in Cs-treated mica-vermiculites by transmission electron microscopy, give information on the morphology and crystal orientation and continuity in individual particles of clay size. Interlayer Cs apparently stretches that part of the silicate sheet in closest proximity and when exchange by Cs is incomplete, warping of the particle occurs. Warping favors the appearance of bend contours in transmission electron microscopic images of the particles. These contours terminate at crystal boundaries within a particle. A specimen tilting stage is useful in bringing the contours into view and in “exploring” individual particles.

Large hydrothermal deposits of halloysite clay occur in the Terraced Hills, Washoe County, Nevada and similar bodies probably are present elsewhere in the Basin and Range province. The host rock, an andesitic tuff, is underlain and overlain by volcanic flows; all these rocks are late Miocene to Pliocene in age. The clay bodies are composed mostly of halloysite with some iron oxides, variable amounts of feldspar and quartz, and locally some montmorillonite. Commonly all the pyroclastic unit is altered to halloysite material. In one locality, however, the halloysite body is restricted to the upper part and it is in sharp contact with underlying, partly montmorillonitized tuff. The contact of a clay body with the overlying basalt is distinct. Generally some halloysite is present in the lower part of the basalt and montmorillonite occurs in both materials near their contact. The solutions that altered the tuff were generated during volcanism, rose along high-angle faults, and were restricted to the permeable and otherwise favorable vitric tuff by the capping of relatively impermeable basalt.

Woolly erionite from the Reese River deposit, Nevada, is identical in appearance to that at the type locality, near Durkee, Oregon. Both of these erionites differ in appearance from all other erionite reported in the past 20 years from diverse rocks throughout the world which are described as prismatic or acicular in habit. The non-woolly erionites are especially common as microscopic crystals in diagenetically altered vitroclastic lacustrine deposits of Cenozoic age. The Reese River woolly erionite fills joints in gray to brownish-gray lacustrine mudstone of probably Pliocene age, in a zone about 1 m thick beneath a conspicuous gray vitric tuff. Compact masses of long, curly, woolly erionite fibers are in the plane of the joint and locally are associated with opal. Indices of refraction are ω = 1.468 and ε = 1.472; hexagonal unit-cell parameters are a = 13.186(2) Å, c = 15.055(1) Å, and V = 2267.1(0.9) Å3. A chemical analysis of woolly erionite yields a unit-cell composition of: Na1.01K2.84Mg0.3Ca1.69Al8.18Si27.84O72·28.51H2O.