Solutions containing AlCl3 and Si(OH)4 (concentrations ≤ 1.5 mM with molar Si:Al ratios of 1:2, 1:1 and 3:1) and FeCl2 (0, 0.5 and 1.0 mM) were adjusted to pH 8 with Ca(OH)2, and incubated at 23°C and 89°C without exclusion of air in the presence of CaCO3 for 8–12 weeks. The products were characterized by infrared spectroscopy and X-ray diffraction. Systems with 3:1 and 1:1 Si:Al ratios without Fe gave hydrous feldspathoids at 23° and 89°C. Systems with 3:1 Si:Al ratios containing Fe gave aluminous nontronites at 89°C and noncrystalline, nontronite-like products at 23°C. Systems with 1:1 Si:Al ratios with added Fe gave Fe(III)-substituted hydrous feldspathoids at 23°C. At 89°C, the system with 1:1 Si:Al ratios and 0.5 mM Fe produced a “protohalloysite,” while that with 1.0 mM Fe gave a poorly ordered nontronite-like layer silicate. In systems with 1:2 Si:Al ratios, the formation of “protoimogolite” at 23°C was little affected by additions of Fe. At 89°C, the “protoimogolite” decomposed to boehmite and poorly-ordered layer silicate phases. Inclusion of 1 mM MgCl2 in the above systems had no effect on the products at 23°C, but at 89°C produced saponites and a mixed layer saponite-chlorite in the 3:1 Si:Al systems, and saponite-like layer structures in the 1:1 and 1:2 Si:Al systems.

Single crystal X-ray diffraction and electron-optical analysis were used to investigate the weathering of a chromium-bearing muscovite (fuchsite). The muscovite had mostly altered to kaolinite with minor amounts of halloysite occurring between kaolinite plates. Evidence for both epitactic and topotactic growth of kaolinite from muscovite was obtained and no intermediate poorly-crystalline phases were detected. About half of the Cr in fuchsite was incorporated into kaolinite, whereas most of the Ti, Fe and Mg was lost.

X-ray diffraction patterns of oriented films of montmorillonite containing enantiomeric tris(2,2′-bipyridyl) ruthenium(II) chloride (Ru(bpy)22+) show a peak corresponding to basal spacings of approximately 27 Å. This peak is absent from the X-ray patterns of montmorillonite films containing racemic cations. A basal spacing of 27 Å is consistent with the adsorption of 2 layers of the enantiomeric cations in each interlayer space. Under the same condition only one layer of the racemic cation was intercalated (basal spacings of 17.9 Å). These results are in accord with previous reports that montmorillonite can adsorb more of the optical isomers than of the racemic mixture of Ru(bpy)32+. Addition of NaCl to the mixtures resulted in an increase in the level of adsorption of the racemic cations and in the appearance of a peak at 27 Å in the X-ray pattern.

The Upper Cretaceous (Maastrichtian) Whitemud Formation is a potentially commercial kaolin deposit located in southern Saskatchewan and southeastern Alberta. The Whitemud Formation contains a lower kaolinitic sandstone, a middle lignite and carbonaceous shale, and an upper interbedded siltstone and claystone. The sediments that comprise the rocks of the Whitemud Formation were deposited on alluvial or upper deltaic plains located along the northwest flank of the Williston Basin.

Mineralogy and textures were determined by X-ray powder diffraction, scanning electron microscopy, and optical microscopy. Kaolinite abundance increases upward from the underlying rocks of the Eastend Formation through the Whitemud Formation, and the abundance of smectite, micas, and feldspars decreases from the Eastend Formation into the Whitemud Formation. Vermiform kaolinite crystals are in close spatial association with feldspar and mica grains. Near the top of the Whitemud Formation, etched quartz and feldspar grains, and gibbsite suggest the presence of a strong chemical leaching environment.

Mineral distributions, presence of root remains, pedologic mottles, grain coatings composed of clay, and soil horizons indicate the Whitemud Formation sediments were modified by intense weathering in a paleosol environment.

Kaolin concentrated from selected kaolinitic sandstone deposits, and beneficiated by oxidation, leaching, and high-intensity wet-magnetic separation has a product brightness up to filler quality. Recovery of lowabrasion kaolin is low and viscosity of a fine-particle kaolin fraction is high. Economics of producing a wet-processed filler-grade kaolin is marginal.

Two distinct zonal sequences of clay minerals (H- and L-type) were found around silicified rocks in the Makurazaki volcanic area, Kagoshima Prefecture, Japan. The clay mineral sequences from the inner to the outer parts of the alteration aureoles are: 1. H-type, pyrophyllite → dickite → 2M2 mica → sudoite → tosudite; and 2. L-type, kaolinite → rectorite → smectite. The structural formula for the sudoite is: (Al1.04Mg1.28Fe3+0.20Ti0.03Li0.01K0.02Na0.01(OH)6Al2.00(Si3.54Al0.46)O10(OH)2. It is characterized by relatively large amounts of Mg and very small amounts of Li. The polytype is identified as IIb. The chemical analysis of tosudite shows that the sample is composed of an interstratification of sudoite-like and beidellite-like layers. The structural formula for rectorite is: (K0.45Na0.19Ca0.01Mg0.01)(Al1.81Fe3+0.04Mg0.13Ti0.03)(Si3.41Al0.59)O10(OH)2, suggesting that the nonexpandable and expandable layers have K-mica-like and beidellite-like compositions, respectively. These clay minerals in the H- and L-type alteration aureoles were formed under relatively high- and low-temperature conditions, respectively, with pH value and K- and Mg-activities increasing as the fluids ascended through the wall rocks.

The effect of layer charge and of the interlayer cations of smectites on the hydrolysis of azinphosmethyl (0,0-dimethyl S-((4-oxo-l,2,3-benzotriazine-3(4H)-yl)methyl) phosphorodithioate) in an aqueous medium was investigated. Ultraviolet spectroscopy was used for monitoring the hydrolysis process. Hydrolysis of the pesticide is catalyzed by Ca-hectorite (layer charge 0.216) but is not catalyzed by Ca-nontronite nor by Ca-montmorillonites with a layer charge above 0.216. The Mg- and Cu-hectorites and Cu-montmorillonite with a layer charge of 0.264 also show catalytic activity. The catalytic activities of the Ca2+ and Cu2+ cations as exchange cations of the smectite and as salts are compared. In agreement with previously reported work, the results show that the hydrolysis of azinphosmethyl may involve the adsorption of the pesticide into the interlayer space of the smectites, forming a bidentate complex with the interlayer cations. This interaction must enhance the electrophilic nature of the phosphorus atom, thereby facilitating its nucleophilic attack by the OH-ion and producing rupture of the P-S bond.

Mixed-layer clays of variable composition and structure occur in core samples from two drillholes (WK207 and WK210) drilled into the Te Mihi sector of the Wairakei geothermal field. These were identified by X-ray diffraction analysis of glycolated and oriented sample fractions at less than 2 μm and less than 0.2 μm.

Low permeability lacustrine sediments encountered by drillhole WK207 contain a well-developed sequence of mixed-layer clays. The shallowest downhole appearance of mixed-layered illite/smectite (I0.6/Sm) occurs at 146 m depth where temperature is only 100°C. Discrete illite is present only below 297 m (200°C) in the finer size fraction (less than 0.2 ¼m). Chlorite first appears downhole, in association with illite-smectite, at 177 m depth (110°C).

Drillhole WK210 encountered predominantly ignimbrites and rhyolites, and fluid flow here is mainly in channels. Within these rocks, a sequence of interlayered clays is poorly developed. Discrete illite and chlorite are present in core from only 244 m (180°), but the measured temperatures where interlayer clays occur ranges from 140 to 209°C.

Differences in the identity of clay minerals present in the Wairakei reservoir, where conditions are otherwise the same, demonstrate the strong control that the type of fluid flow has on their formation. In poorly-permeable sediments, where diffuse fluid flow prevails, a clearly-defined sequence of mixed-layer clays occurs. These are absent where channel flow dominates, the discrete chlorite and illite deposit directly from solution.

Weathering has etched and deeply-denticulated the constituent orthopyroxenes, and chlorite has been transformed to vermiculite in the upper 3 m of an aeolian, periglacial sand dune formed in northeastern Indiana about 13,000 b.p. Pyroxene weathering begins with the development of cleavage-parallel etch pits on {010} and {100} surfaces. These pits coalesce and eventually crop out on basal surfaces as denticulations. The mean denticulation size increases logarithmically toward the surface, and the denticulation size of the orthopyroxenes is a quantifiable feature of the weathering process. Ferruginous pendants, microboxworks of iron oxides, and other indications of iron redeposition within the ortho-pyroxene microenvironments were not observed.

Chlorite in the dune has been weathered to vermiculite. The parent chlorite is a high-Fe variety, and the transformation to vermiculate does not involve the development of a chlorite/vermiculite intermediary phase. Fe2+ is oxidized as part of the transformation process and this iron is retained in the sediment as discrete goethite and as crystalline and noncrystalline coatings on the dune grains. The vermiculite from depths shallower than 64 cm is only partly expandable and is completely collapsed by K-saturation or heat treatment. This is a hydroxy-Al vermiculite and its formation is typical of intense weathering under the acid conditions prevalent at the dune surface.

New pillared clay-based adsorbents have been prepared by incorporating a nonionic surfactant of general formula C12–14H25–29O(CH2CH2O)5H (commercial name, Tergitol 15S-5), during the synthesis of the aluminum hydroxide pillaring reagent. Different loadings of surfactant have been examined. The presence of the surfactant enhanced the adsorption capacity of the clay toward 3-monochlorophenol from aqueous solution. On the basis of adsorption results for a series of clays with increasing surfactant loadings, the best adsorbent was obtained at a surfactant loading of 255 mg/g of clay. At this loading, the surfactant occupies the micropores, as well as the mesopores and the external surfaces of the pillared clay. Analysis of the adsorption isotherms for 3-monochlorophenol, 3,5-dichlorophenol, 3,4,5-trichlorophenol and pentachlorophenol at different pH shows that the most energetic adsorption sites are the surfactant-occupied micropores between pillars. Additional binding of chlorinated phenols occurs at surfactant sites on external surfaces and mesopores. Upon calcination at 500°C, the clay is converted to a conventional alumina-pillared clay with a basal spacing near 16 Å. This calcined product can be reused as an adsorbent for chlorinated phenols by readsorbing fresh surfactant. The recycled adsorbent exhibits performance properties comparable to the original adsorbent. These results demonstrate the feasibility of utilizing a surfactant-modified pillared clay as a recyclable adsorbent and combustion catalyst for environmental pollutants.

The literature reports that freezing of aqueous aluminosilicate clay suspensions can produce clay aggregates that disperse with agitation. Our experiments indicate that colloidal suspensions extracted from north Idaho loess soils (Boralfs), when frozen, form silt- and sand-sized agglomerates that resist dispersion with agitation. XRD and TEM analyses showed that colloids are dominantly halloysite between 0.10 to 0.30 μm in diameter. The colloidal halloysite has anomalously high mole ratios of Si/Al and a high Fe content. Freeze-produced agglomerates are light yellow to yellowish-brown in color, occur in the form of plates, wedges, cuspates, or laths, and often exhibit uniform optical properties, suggesting a crystalline product. Selected area electron diffraction, however, indicates that the agglomerates are polycrystalline. With proper orientation, agglomerates produce acute bisectrix interference figures that are optically negative with variable 2V, generally <30°. XRD analyses and IR spectra imply that the agglomerates are halloysite. Measured optical properties, however, are difFerent than those reported for halloysite and may be affected by the high Fe content and polycrystalline nature of the agglomerates. Grains, exhibiting similar optical properties as laboratory-produced agglomerates, are a minor proportion of the very-fine sand fraction in some horizons of the soils studied. Freeze-aided agglomeration of colloidal material may be an important process in temperate climates. It may be overlooked because of particle destruction by soil pretreatments or morphological order and/or optical similarity to some micaceous minerals.

Infrared spectra of adsorbed pyridine have been used to obtain qualitative information on the nature of the interaction of pyridine with different rhodium catalysts supported on palygorskite and silica. Based on these data, qualitative definitions of the adsorption sites of these catalysts have been deduced. The catalysts were prepared with natural palygorskite, and palygorskite dehydrated in vacuo at 150°C and 400°C. In this way, catalysts were obtained that had different water contents and, therefore, different acidities. Lewis-bound pyridine was detected by infrared spectroscopy from room temperature to 500°C. The greatest acidity was found in a catalyst prepared with the palygorskite support dehydrated at 150°C before preparation of the catalyst. With this catalyst, strongly hydrogen-bound pyridine was observed when evacuation was carried out at temperatures between 150°C and 300°C. Catalysts prepared with the palygorskite support pretreated at 400°C did not exhibit strongly hydrogen-bound pyridine, and Lewis acidity decreased significantly. As expected, hydrogen-bound pyridine was also detected for rhodium supported on silica. However, it was desorbed at temperatures below 150°C. The results of the acidity studies follow the same pattern as those for 1 -hexene double-bond migration under hydrogénation reaction conditions.