Samples of nacrite, dickite, kaolinite, and halloysite were investigated using X-band electron paramagnetic resonance (EPR) and Mössbauer spectroscopy. Fe3+ gave rise to EPR signals at g ≃ 4 which differed with the individual polytype. Only nacrite had no resonance in this region of the spectrum, but it had one at g ≃ 2. Dickite had a quadruple line, kaolinite a triple line, and halloysite a single line in this region. The EPR spectra of these minerals are apparently dependent also on the orientation of adjacent layers in the structures. Other resonances were attributed to (1) clusters of ferric ions giving rise to broad resonance near g ≃ 2, (2) trapped holes, and (3) free radicals linked with organic matter. The Mössbauer spectroscopic results suggest that iron occurs in the ferric state (except in nacrite where Fe2+ is present also) as an ionic substitution (IS) in octahedral layers. This suggestion follows from the difference is the IS values between octahedral and tetrahedral symmetry sites occupied by Fe3+ equal to ∼0.4 mm/sec. Linewidths depend mainly on the way the layers stack; for monoclinic modifications represented by nacrite and dickite, the linewidths are narrow (Γ = 0.45 mm/sec and 0.56 mm/sec, respectively); pseudomonoclinic halloysites also gave narrow linewidths (Γ = 0.39 mm/sec and 0.48 mm/sec). The widest line was observed for triclinic kaolinite (Γ = 0.62 mm/sec and 0.71 mm/sec).

The rate of dissolution of phlogopite in an open system was measured at low temperature and pressure and at pH 3–5. The maximum dissolution rate was achieved by maintaining extremely low ionic concentrations in the solution using a cation-exchange resin (hydrogen form) as a trap for released cations. The resin also served as a source of hydrogen ions and acted as a buffer. The concentrations of ions adsorbed on the resin and remaining in solution were measured, along with surface area and cation-exchange capacity. The amount of phlogopite dissolved after 1010 hr was 67 times that dissolved using a CO2-buffered, closed-system method. During the first hour of the experiment, dissolution was incongruent, but later became congruent from 1 to 1010 hr. From 1 to 200 hr the reaction had linear kinetics. The dissolution rate for the first 200 hr of the reaction was 2.0 × 10−14 mole KMg3AlSi3O10(OH)2/cm2/sec. Since no evidence of parabolic kinetics was found, there is no reason to postulate the formation of a “protective layer.”

The crystal structure of natural boehmite, AlOOH, from Tveidalen, Langesundsfjorden, Norway, with a = 3.693(1), b = 12.221(2) and c = 2.865(1) Å, was refined from single crystal X-ray diffraction data (MoKα maximum 2θ = 120°) to an Rw value of 0.032 in space groups Amam and A21am. In both cases the proton was found to occupy positions of the type (x, 0.038, 0), where x = 0.104 and 0.396, about 0.75 Å from the donor oxygen atom. This arrangement corresponds to the presence of chains of asymmetric hydrogen bonds with random polarity parallel to the a axis, and indicates that the effective space group is Amam. No significant electron density was observed either at the center (0, 0, 0) or at the position (1/4, y, 0), corresponding to symmetric and bifurcated hydrogen bonds, respectively, between the layers of octahedra.

Calculations of the total energy of a representative portion of the boehmite structure as a function of hydroxyl orientation, using semiempirical molecular orbitals of the Hückel type, are in agreement with the observed electron density distribution and suggest a preference for (1) sp3, rather than sp2, hybridization of the donor oxygen atom orbitals, and (2) asymmetric, rather than symmetric hydrogen bonds. Disorder of the hydrogen atom positions within individual hydrogen bond chains is shown to be much less likely than disorder between adjacent fully coherent chains.

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.

Trioctahedral smectite and regularly interstratified chlorite/smectite in strata of the East Berlin Formation of the Connecticut Valley are largely restricted to black shale and gray mudstone deposited in alkaline, perennial lakes. The precursor of the mixed-layer clay appears to have been a smectite. Alkaline lake waters and inherited pore waters rich in magnesium favored the transformation of smectite to mixed-layer chlorite/smectite by fixation of brucitic interlayers into the smectite unit structure. Gray mudstones containing the mixed-layer chlorite/smectite are invariably underlain by magnesium-rich black shale—a possible source of Mg for the clay mineral transformations. The black shale is composed predominantly of Mg-rich trioctahedral smectite of probable authigenic origin.

Boron adsorption by Ca forms of montmorillonite, illite, and kaolinite was determined as a function of pH and boron concentration in solution. Data from batch experiments were compared with results computed for each clay according to fitted adsorption coefficients (maximum boron adsorption and affinity constants related to the binding energy). The agreement between calculated values and experimental results indicates that a phenomenological equation can be used to predict boron adsorption on clays as a function of both of these variables. For the solution-to-clay ratios examined, the water content does not affect the boron-surface interaction as expressed by the above adsorption parameters. Because the affinity of clays for B(OH)4− is much stronger than for B(OH)3 , the adsorption maximum was obtained only under alkaline conditions at approximately pH 9.0 to 9.7. It is suggested that the pH of maximum adsorption is a function of the ratios of affinity coefficients of the three species B(OH)3, B(OH)4−, and OH− competing for the same adsorption sites. The adsorption coefficients indicate that in some cases the difference in the amount of adsorbed boron between montmorillonite and kaolinite could be either small or large, depending on the circumstances. The main factor that would affect this difference is the total amount of boron in the suspension. Estimated value of the adsorption maximum was 2.94, 11.8 and 15.1 µmole/g for Ca-kaolinite, Ca-montmorillonite, and Ca-illite, respectively.

Well-crystallized laumontite has been found for the first time precipitating naturally at the earth's surface at temperatures of 89° to 43°C as a component of gray to white coatings and efflorescences on exterior surface and as precipitates on interior fractures of stones and blocks lining Hot Springs Creek immediately downstream from Sespe Hot Springs, Ventura County, California. X-ray powder diffraction, scanning electron microscope (SEM), and electron microprobe analyses show thenardite to be the dominant phase in the exterior coatings, in association with minor microcrystalline (<50 μm) laumontite and gypsum. Macrocrystalline (>1 mm) laumontite is the dominant phase in interior fracture coatings and is associated with quartz, potassium feldspar, and gypsum. Trace amounts of smectite(?), halite, a mercury sulfide, an iron sulfide, an iron-bearing mineral (possibly an oxide or carbonate), and a copper mineral are also present. Zeolites other than laumontite have not been seen, and carbonate minerals are either entirely or nearly absent. SEM textures indicate nonreactive intergrowths of laumontite, quartz, potassium feldspar, and gypsum. Unbroken laumontite crystals are generally euhedral or have skeletal growth characteristics and exhibit sharp, fresh, non-corroded faces, edges, and corners.

The water issuing from the hottest and largest spring is 89°C, has a pH of 7.74, 1200 mg/liter total dissolved solids, and contains Na+, Cl−, SO42-, and H4SiO4 as the dominant dissolved species. Computations indicate that the water is supersaturated with respect to laumontite, quartz, chlorite, and prehnite and is slightly undersaturated with respect to calcite and noncrystalline silica. Water-dominated water-rock interaction is indicated by isotopic analyses. The δO18 composition expectable on the basis of the −81‰ δD composition is −11.38‰ instead of the −9.5‰ actually found (all referred to SMOW). The water chemistry suggests that the subsurface water source may have a temperature of 125°–135°C. This temperature range, together with the regionally low geothermal gradient, implies that the source is probably 3550 to 3900 m beneath the springs in fractured and permeable Mesozoic and older plutonites and gneisses.

The discovery of laumontite crystallizing at atmospheric pressure and 43°C (or lower) provides important insight into the processes responsible for burial diagenetic laumontite and a valuable perspective on the zeolite metamorphic facies.

Noncrystalline aluminosilicate gels with Al2O3/(Al2O3 + SiO2) weight ratios from 0.3 to 0.5 were reacted in 0.1 N KOH at temperatures varying from 125° to 175°C. The pH of the solutions dropped sharply with increasing gel:solution ratios, indicating that the coordination number of Al in the products changed from IV to VI. The degree of hydrolysis appeared to be higher with KOH than with NaOH. X-ray powder diffraction and infrared spectroscopy showed that disordered kaolinite was the only crystalline product formed. Thermal data and surface area measurements indicated that the kaolinite was formed by a condensation process.

The sand and silt fractions of soils derived from Tertiary basalt in northeastern Ireland exhibit unusually high cation-exchange capacities. Smectite was identified by X-ray powder diffraction in all size fractions and was selectively dissolved by treatment with 1 N HCl and 0.5 N NaOH. Structural formulae, based on chemical analysis of the dissolved material, suggest that the smectite is intermediate in composition between a di- and a trioctahedral mineral and that the octahedral cation occupancy, together with the numbers of Mg and Fe atoms per unit cell, decreases with decrease in particle size of the soil fraction examined. The mean formula for the smectite in the clay separates is:

M+0.40(Si3.33Al0.67)(Al1.07Fe2+0.09 Fe3+0.41Mg0.82)O10(OH)2.

Similar analysis of smectite present in clay-size material separated from weathered basalt rock taken from the bases of the soil profiles showed that it had close to the full trioctahedral occupancy. It is suggested that the soil smectite is a weathering product of the trioctahedral smectite inherited from the weathered basalt.

K-bentonites of the Middle Ordovician High Bridge Group along the Cincinnati arch are characterized by interstratified illite/smectite (I/S) clays with rectorite-type ordering. Approximately 20% of the layers are expandable. They are structurally similar to I/S formed at temperatures exceeding 100°C during burial diagenesis, however stratigraphic evidence and a color alteration index of < 1.5 for conodonts in associated carbonates reveals they have never been deeply buried or subjected to temperatures greater than 80°C.

Whole-rock samples of K-bentonites contain ∼8% K2O and ∼4% MgO, whereas the <0.1-µm size fraction contains 6–7% K2O and 5% MgO. By comparison with a hypothetical parent ash, these values represent a net gain of K and Mg and a net loss of Si, Fe, Ca, and Na during post-depositional alteration. K-fixation is accounted for by a layer charge imbalance arising primarily out of octahedral substitution of Mg+2 for Al+3, indicating that the interstratification evolved from a montmorillonite precursor. The chemical characteristics of I/S layers in K-bentonites developed early during the alteration of volcanic ash to montmorillonite. Relatively high contents of K and Mg probably reflect both seawater and parent material composition at the time of formation. The composition and ordered stacking in K-bentonites was determined by the composition of the original smectite rather than by the pressure-temperature conditions of burial diagenesis.

Di-ethyl 2-hexylphosphoric acid (di-2 EHPA) was chemisorbed on kaolinite and smectite in decane solution. The resultant isotherms were of the Langmuir type and made possible the determination of limiting adsorption values of 12 mg/g and 23.8 mg/g on H+-kaolinite and H+-montmorillonite, respectively. The acidic phosphoric group of the di-2 EHPA molecule reacted in the anionic form (RO)2PO2− with the surface cations of the clay structures. Theoretical calculations, based on structural considerations, are in agreement with the experimental data and show that adsorption took place at the rate of one alkylphosphate anion per surface cation if the phyllosilicate was dioctahedral (e.g., montmorillonite and kaolinite). If the phyllosilicate was trioctahedral (e.g., hectorite), adsorption took place at the rate of two di-2 EHPA molecules for three surface cations. Spectroscopic investigations performed with visible, ultraviolet, and infrared radiation confirmed the formation of salts or surface complexes.

Two diagenetic stages of zeolitic alteration were recognized in a study of a thin bed of rhyolitic ash that was deposited in Eocene Lake Gosiute (Laney Member of the Green River Formation). The ash bed can be traced for 30 km along strike and represents a single volcanic event. The bed was not buried deeply (<100°C), and originally it was compositionally homogeneous. Initially, the bed altered to clino-ptilolite, heulandite, an intermediate phase between these two zeolites, and mordenite. These early reactions involved the hydration and solution of glass by saline, alkaline solutions and the subsequent precipitation of zeolites. The variation in zeolite mineralogy is due to differences in interstitial fluid chemistry that resulted from either fluctuations in lake-water chemistry or the proximity of spring discharge. These reactions, exclusive of the addition of H2O, involved only minor amounts of mass transfer over very small distances. Later, after burial, the early-formed zeolites reacted with upward moving sodium carbonate brines that were produced by dewatering of underlying evaporite deposits. The sodium carbonate brines, in equilibrium with trona and nahcolite, elevated the activity of Na+ and produced analcime. These later dehydration reactions involved significant mass transfer.

Monoionic K- and NH4-smectites saturated with ethylene glycol form mixed-layer structures which usually consist of three kinds of layers: a 10-Å, non-expanded layer; a 14-Å, partly expanded layer; and a 16.8-Å, completely expanded layer. In some samples, the 14-Å layers formed 60–70% of all layers present. When saturated with water vapor the smectites commonly consisted of three kinds of layers (10-, 12.6-, and 15.5-Å). Generally these samples contained fewer expanded layers than those saturated with ethylene glycol. This result is attributed to the smaller dipole moment of water compared with that of ethylene glycol. The greater solvation energy of NH4+ in comparison with that of K+ causes the expansion of a part of layers which did not expand in the K forms. This result indicates that there is an inhomogeneous distribution of layer charge in the smectite structure. The prevalent type of mixed layering in the studied samples is that of random distribution of layers.

Allophanes with SiO2/Al2O3 molar ratios from 1.38 to 1.92 were heated at temperatures up to 500°C, and the changes induced were investigated by means of infrared spectroscopy (IR) and X-ray powder diffraction (XRD). Heat treatment caused the IR absorption band near 1000 cm−1 due to Si-O stretching to shift towards higher frequencies, and the band near 450 cm−1 due to O-Si-O bending to increase markedly in intensity. These results are probably due to condensation of SiO tetrahedra, following breakdown of Si-O-Al linkages and dehydroxylation of SiOH groups. Concurrent intensity increase of the IR absorption at about 700 cm−1 suggested an increase in the amount of 4-coordinated Al in the heated materials. ‘Imogolite structures’ were decomposed progressively at higher temperatures and were almost absent at about 400°C, as indicated by the weakening and disappearance of the IR band at 348 cm−1 and of the XRD reflections at 2.25 and 1.40 Å. The XRD reflection at 3.3–3.45 Å shifted to about 3.6 Å, probably as a result of thermal condensation of the silica component. The observed thermal changes were much greater for samples with low SiO2Al2O3 ratios (1.38–1.51) than for those with high ratios (1.81–1.92), indicating a lower thermal stability for the former materials. Thus, the thermal stability of allophanes appears to be related to the content of ‘imogolite structures’ and to the polymerization status of the silica component.

Adsorption studies indicate that paraquat, diquat, and thionine are bound on bentonite by amounts greater than the measured cation-exchange capacity (CEC) of the clay. Methylene blue, new methylene blue, and malachite green are bound by amounts equal to the CEC. The unipositive organocations form aggregates on the clay surface. Aggregation increases with ionic strength and increases the apparent adsorption capacity by 25%. The aggregates are removed by washing with distilled water. Desorption studies show that the dyes are irreversibly bound, whereas the dipositive organocations are reversibly bound. Ionic strength variation reduces adsorption by 15 and 36% in the monovalent and divalent organocation-clay systems, respectively. In the clay-divalent organocation systems adsorption is greater on Na-saturated clay than on K-saturated clay. Adsorption is unchanged over the pH range 4.5–8.5 and decreases steadily below pH 4.0. Changes in adsorption due to changes in temperature are small. The study indicates that ionic strength is the most important variable in clay-organocation interactions.

Three samples of bluish chromium-bearing dickite and chromium-bearing kaolinite were examined by X-ray powder diffraction, chemical analysis, electron microprobe, optical, and infrared techniques to determine whether chromium is part of the mineral structure or present in an impurity phase. Two of the samples studied contain a single dominant chromium-bearing phase (either dickite or kaolinite); the third contains equal proportions of both minerals. The optical absorption and infrared spectra are consistent with the presence of octahedrally coordinated chromium. The range of Cr3+-Al3+ substitution is rather limited: up to 0.06 atoms per unit cell. The electron microprobe study revealed the presence of very rare, minute grains of chromite, as well as a uniform distribution of chromium in dickite and kaolinite, indicating that chromium occupies octahedral sites in the structure of these minerals.

Intercalation compounds of styrene and quaternary ammonium montmorillonite were prepared by immersion of the clay in styrene monomer. The intercalation of stearyltrimethylammonium (CH3(CH2)17N(CH3)3+)-montmorillonite and styrene showed an expansion of the basal spacing to a constant value of ∼32 Å after immersion for 10 days. After polymerization, the amount of polystyrene in the interlayer region was determined by thermal gravimetric analysis. Styrene adsorption initially increased with increasing quaternary ammonium cation and then became approximately constant when loading of the quaternary ammonium cation exceeded 100 meq/100 g clay. The volume resistivity of the stearyltrimethylammonium-montmorilionite-polystyrene complex, which was determined with a high resistance meter, was greater than that of both the quaternary ammonium-montmorillonite and the montmorillonite, and increased in proportion to the amount of polymer adsorbed. These data indicate that polystyrene improved the insulating properties of the clay films.

Mixed-layer illite/smectite (I/S) was formed by reacting the Chambers or Polkville montmorillonite hydrothermally at 270° and 350°C from several hours to more than 15 weeks. Reactions were conducted in closed vessels containing K or mixed K-Na, K-Ca, or K-Mg solutions of varying concentrations. The reaction rate and the rate of ordering of I/S for the reaction smectite + K+ → mixed-layer I/S + SiO2 was inhibited by the addition of Na+ Ca2+, and Mg2+; the inhibitory strength of Na+, Ca2+ and Mg2+, on an equivalent basis, increased approximately in the ratio 1:10:30. The first order reaction-rate constants for the reactions at 270° and 350°C indicate an activation energy of about 30 kcal/mole.

In the experimental system studied, the reaction smectite → mixed-layer I/S appeared to proceed by solid state transformation, as suggested by: (1) rapid dissolution of large amounts of silica, probably creating an Al-enriched residue; (2) similarity of particle size and morphology of the mixed-layer products to those of the original montmorillonite, implying no extensive dissolution of Al3+; and (3) relatively high activation energy compared to published values for silicate dissolution.