Sodium-saturated Wyoming bentonite was hydrothermally reacted at 150° and 250°C for 30 to 180 days to determine smectite alteration rates that might be applied to nuclear-waste repository design. Na-Ca solutions deficient in K were used to determine the role of interlayer cations in the creation of high layer-charge in the smectites. The results provide insight into the mechanism and timing of various steps in the diagenetic alteration of smectite to illite. X-ray powder diffraction (XRD) analyses of the reacted clay showed little effect on the character of the 17-Å reflection even after 180 days at 250°C. Potassium saturation of these reacted clays and re-examination by XRD indicated collapse of some smectite layers, leaving at most only 60% expandable layers. The development of layer charge sufficient to cause collapse on saturation with a low hydration energy exchange-cation does not require K in the reacting fluid. Rate constants for the illitization reactions as determined by K-saturated collapse are between 1.0 × 10−3 and 2.8 × 10−3/day with activation energies <3.5 kcal/mole. Ca in a Na-silicate-bicarbonate solution slightly reduced the illitization rate constants. These rate constants are higher than expected from extrapolation of studies of beidellite-composition glasses at higher temperatures, but lower than values obtained in studies of natural clays in artificial sea water. The release of Si, Al, and Mg in the 150°C experiments suggests congruent dissolution of the smectite. In contrast, at 250°C the release of Al was not stoichiometric with Si; as little as one half of the relative available Si was released. Rather than different mechanisms for dissolution at the two temperatures, the conclusion is that noncrystalline Al-rich phases formed at greater rates at higher temperatures. The cation-exchange capacities for several of these reacted smectites were significantly less than expected, suggesting a clogging of interlayer sites, perhaps by Al-complexes.

Reaction of hydroxy-Al oligocations with Ce3+- and La3+-exchanged montmorillonites, using 1.25, 1.60, or 2.0 mmole Al/g smectite, yielded partially pillared hydroxy-Al montmorillonite products containing a significant concentration of residual Ce3+ or La3+. After heat treatment at 250°C these products showed high surface areas (∼340–500 m2/g) and high basal X-ray powder diffraction spacings (18.0–18.6 Å). Calcination at 400°–700°C resulted in lower surface areas of ∼200–450 m2/g and basal spacings of 16.3–18.3 Å, the values showing a gradual decrease with a decrease in the Al/smectite weight ratio and/or increase in the heat-treatment temperature. A major modification and improvement in the cross-linking procedure was achieved by fast aging (6–48 hr) of the hydroxy-Al oligomeric solution at 95°–100°C, instead of conventional aging for 2–3 weeks at 25°C.

Fluorinated NH4+-montmorillonites, containing 0.4 to 2.1 wt. % F, were prepared by reaction of NH4+-montmorillonite at 60°C with 1.0 to 3.0 N aqueous solutions of NH4F. Interaction of the fluorinated montmorillonites with hydroxy-Al oligocations, using a ratio of 2.0 mmole Al/g smectite, yielded a series of cross-linked fluorinated montmorillonites with basal spacings of 17.9–18.0 Å and surface areas of 180–325 m2/g after heat treatment at 250°C. Calcination at 400°–500°C resulted in lower d(001) (16.6–17.7 Å) and surface-area values (140–300 m2/g). Increase in the fluorine content caused gradual decrease in both values. Transmission electron microscopy of pillared Ce-montmorillonite showed a highly oriented network of well-separated, parallel unit layers with an interlayer distance, Δd(001), of 9–10 Å. Calculated lateral (interpillar) distances were in good agreement with the pore-size distributions determined in independent adsorption studies.

Mineralogy, kaolin crystallinity, Fe content, δO18, and δD were determined for late Cretaceous “soft” and early Tertiary “hard” Georgia kaolins. The crystallinity of the <0.5-, 0.5–1.0-, and 1.0–2.0- μm size fractions of soft kaolins was higher than that of equivalent size fractions of hard kaolins. δO18 and δD of the soft and hard kaolins ranged between 18.5 to 23.1‰, and −64 to −41‰, respectively, and could not be used to discriminate soft from hard kaolins. The trends of crystallinity vs. δO18 were different for kaolins collected at different localities, and, for a given sample, δO18 generally decreased with increasing crystallinity and with increasing crystallite size. These data indicate that the Tertiary kaolins could not have been simply derived from the Cretaceous kaolins by winnowing unless post-sedimentation recrystallization of one or both occurred. δD vs. δO18 systematics indicate that the late Cretaceous to early Tertiary Georgia kaolins crystallized over a temperature range of about 15°C in the presence of waters that varied little in isotopic composition.

A program of simultaneous linear equations has been developed to calculate component proportions and/or component property values for mineral mixtures in soil clays and sediments. The analysis is based on quantitatively measured chemical and physical properties of samples and involves (1) qualitative identification of the mineral components in the mixture by any appropriate means; (2) quantitative measure of the sample property values selected for use in the program; (3) estimation of the proportion of each component in the mixture by a technique such as X-ray powder diffraction; (4) assignment of limits to component property ranges; (5) selection of one of four available calculation options and application of the simultaneous linear-equations program; (6) examination of the residuals of the analysis and, if appropriate, adjustment of the initial estimates for component proportions or property ranges and then repeating step 5; and (7) verification of the final component proportions by comparison with information from step 1. Completeness and/or accuracy of the final results for component proportions may be checked by the closeness of approach to 1.0 for the sum of the component proportions. The method requires that, at minimum, the number of properties measured must equal the number of components in the samples being analyzed and that the minimum number of samples must equal the number of properties measured.

Using the clay fractions of 15 Pennsylvania soils containing kaolinite, illite, smectite, vermiculite, chlorite, interstratified vermiculite/chlorite, quartz, and noncrystalline material, and measuring methylene blue cation-exchange capacity, the amount of Ca displaced by Mg from a Ca-saturated clay, the amount of K displaced by NH4 from a K-saturated clay heated to 110°C, % K2O, % SiO2, % MgO, and weight loss at 110°–300°C and 300°–950°C, the adjustment of property values was found to have the lowest residual value and the most consistent results. The source of analytical errors was also located by examination of residual tables. Samples that were similar in composition gave more reliable component proportions.

The sorption properties of Co, Cu, Ni, and Ca were studied in a mixed mineral suspension of synthetic MnO2 and Wyoming montmorillonite. The distribution of the sorbed cations between the two solid phases was measured by indirect chemical fractionation with acidified NH2OH-HCl and by direct X-ray spectroscopic analysis of mineral particles using electron microscopy. Electron microscope and NH2OH-HCl measurements of the quantity of Co sorbed on MnO2 agreed within 6%. Seventy-seven, 67, and 69% of the total Co, Cu, and Ni sorbed by the mixed mineral suspension was found on the manganese oxide. The opposite distribution was found for sorbed Ca with 28% on the manganese oxide and 72% on the montmorillonite particles. The observed differences in metal sorption by these minerals are related to the cation-sorption mechanisms of manganese oxide and montmorillonite.

Reactions of smectite with phenols were investigated to understand the role of clay minerals in abating transport of these organic pollutants to ground water. Sorption of o-methylphenol, o-chlorophenol, and m-methylphenol by the clay with different exchange cations was accomplished by passing phenol vapors in a slow stream of air or nitrogen through the samples. The resulting products, extracted with methanol and analyzed by using mass spectrometry, included monomers, dimers, trimers, and tetramers of the parent phenol and of the corresponding quinones, the oxidation product of the phenols. In extracts from the Fe-clay-phenol complexes formed in air, traces of the phenolic pentamers were also detected. Both sorption and polymerization were much higher in air than in nitrogen. The greatly reduced polymerization in nitrogen suggests that anaerobic environment of the landfill sites may facilitate phenol transport to ground water. The degree of polymerization and its magnitude was in the order Fe- > Al- > Ca- > Na-clay.

A corrensite-like mineral, from near Borgotaro, Parma (Taro Valley, Italy), was studied by X-ray powder diffraction (XRD) and thermal analysis at different temperatures and water vapor pressures in the natural state and after exchange with ten different cations. In the natural state the mineral is characterized by a basal reflection at ∼29 Å shifting to ∼24 Å on heating and to ∼32 Å by glycerol treatment. The dehydration features of the homoionic minerals show that the stability of the complex of water, compensating cation, and silicate framework depends on the electrostatic energy of the water dipole in the cation field, similarly to smectite.

XRD of the exchanged mineral shows a basal reflection of ∼58 Å particularly in the NH4-, Rb-, and Ba-exchanged states. This value suggests a structure characterized by a regular sequence of silicate layers with different layer charge, that generally results in a c periodicity of ∼29 Å, but which shifts to ∼58 Å, and perhaps higher values, because of small differences in the compensating cation layers.

Zeolites and associated minerals occur in a tholeiitic basaltic pillow lava sequence that makes up part of the Eocene Siletz River Volcanics in the central Coast Range, Oregon. Regional zoning of zeolite assemblages is not apparent; the zeolites formed in joints, fractures, and interstices, although most occur in central cavities of basalt pillows. The zeolites and associated minerals identified, in general order of paragenetic sequence, are smectite, pyrite, calcite (small spheres), thomsonite, natrolite, analcime, scolecite, mesolite, stilbite, heulandite, apophyllite, chabazite, mordenite, calcite (scalenohedra and twinned rhombohedra), laumontite, and amethystine quartz. Common three-mineral assemblages are: natrolite-analcime-stilbite, stilbite-heulandite-chabazite, stilbite-apophyllite-chabazite, and natrolite-mesolite-laumontite.

Alteration of basaltic glass, which was initially abundant, appears to have been an important factor in formation of the zeolites. Isotopic data suggest that zeolitization occurred during a low-temperature (60°–70°C) submarine hydrothermal event, or by reactions of cold (∼10°C) meteoric water with basalt over a long time. The occurrence of different mineral assemblages in cavities of adjacent basalt pillows indicates that these minerals crystallized in closed systems that were isolated as fractures and joints were sealed by deposition of smectite and early zeolites. Although the total chemical composition of the mineral assemblages in cavities is similar, different mineral species formed because of the sensitivity of zeolite minerals to slight variations in physical and chemical conditions within individual cavities.

The Cs selectivity of several natural zeolitic tuffs and synthetic zeolites was measured. Phillipsite-rich tuffs from California and Nevada exchanged 13.5 and 23.7%, respectively, of the Cs present in simulated alkaline defense waste containing 0.00025 M CsCl in 5.5 M NaCl-NaOH solution from the Savannah River Plant, Aiken, South Carolina; whereas mordenite-rich tuffs from Arizona and Nevada exchanged less than 12.7%. The immobilization or fixation of Cs in phillipsite unlike other zeolites can be achieved by heating the zeolite at 600°C for 4 hr in air and collapsing the silicate (aluminate) tetrahedral rings around the Cs ions to produce a Cs-feldspar-type phase. Treatment of the Cs-exchanged phillipsite-rich tuff at 800° to 1000°C resulted in pollucite, CsAlSi2O6, which also “locks in” the Cs ions in its structure. The fixation of Cs exchanged in phillipsite can also be achieved by the formation of pollucite upon hydrothermal treatment at 300°C and 30 MPa pressure within 12 hr. These results suggest that phillipsite-rich tuffs are good candidates for Cs immobilization by heat treatment at low temperatures after they have been used as sorbents in waste decontamination.

Iron salts react readily with calcite in oxidizing calcareous environments to produce solid phase Fe-oxides. These reactions represent important processes in aqueous, geologic, and pedogenic environments. In the present investigation, Fe-oxides were precipitated from Fe(ClO4)2 solutions on undisturbed calcite grains in aqueous suspension. In this way it was possible to investigate the sequence of events in the crystallization process. Following an initial precipitation on the calcite grains, a period of slow growth of lepidocrocite was noted wherein 4-μm euhedral platelets formed with uniform orientation perpendicular to the calcite surface. The slow growth and highly crystalline nature of the Fe-oxide product may be partially due to the diffusion barrier formed by the growing oxide crystal mass which influenced rate of movement of HCO3− to the dissolved Fe phase and Fe ions and H+ towards the calcite surface. Upon continued aging, the supernate became noticeably opaque. As the suspended nuclei settled, new surfaces for crystal growth were provided which resulted in somewhat less crystalline lepidocrocite and goethite.