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Single grain X-ray and electron diffraction patterns of weathered biotite flakes exhibit groupings of 001 and hk reflections of biotite, vermiculite, mixed-layer clay minerals, and kaolinite indicating that the secondary minerals are in parallel crystallographic orientation to the parent biotite. Asterism of biotite reflections is enhanced by weathering. Gibbsite crystals developed in parallel basal orientation to biotite flakes. Most goethite in weathered biotite occurs as aggregates of randomly oriented crystals in cleavages and on grain surfaces. Some goethite is present on micaceous fragments as 0.05-μm size, lathlike crystals in a hexagonal arrangement with their (100) face resting on the (001) biotite face. Selected area electron diffraction patterns of aggregates of lathlike goethite crystals contain 0kℓ, 1kℓ, and 2kℓ reflections due to undulation of the aggregates and the extreme thinness of the crystals. These patterns indicate that the close packed anion layers in goethite coincide with the brucite-like layer of the micaceous minerals.
Total, slightly, and highly swelling clay minerals can be separated and measured by the test procedure described. Separations of synthetic mixtures of essentially pure natural sediments indicate that the measurements are accurate within ± 1% of the true values for samples containing < 20% swelling clays, and that < 1% quantities can be detected. Test results using < 5 micron material show that small grain size is not a problem in effective separation.
The test procedure is primarily a centrifuge separation based on the hydrated grain densities of the swelling clay minerals. The sample grains are pretreated with silicone (Dow 1107). The swelling clays are separated from rock and soil samples by centrifuging the sample-water slurry over a non-water-miscible heavy liquid. The sample is stirred violently at and above the water-heavy liquid interface during this centrifuging. The desired swelling clay fraction is recovered in the water medium and the denser minerals are collected in the heavy liquid. Water-soluble minerals are removed by filtering. Quantitative measurements are based on dry weights.
Application of this method to petroleum engineering and geology is stressed, but other disciplines will have use for the described procedure.
The term “flint clay” used in USA and several other countries, corresponds very closely to the term “toasted bread (sukhar) clay”. In both USA and U.S.S.R., the typical occurences of “toasted clays” are confined to deposits of the lower Carboniferous. In their properties and occurrence the well-studied toasted clays of the Borovichy deposit (Novgorod province) are highly similar to the flint clays of Missouri, differing significantly only in having lower bulk specific gravity and higher porosity than do Missouri flint clays. Varieties with excess free alumina (diaspore, boehmite) are observed both among “toasted” and flint clays. The author suggests the term “toasted complex” (sukharnii kompleks) which corresponds to W. D. Keller’s term “flint clay facies”. The clays of the “toasted complex” are sediments of ancient swamps and lakes which contained rich vegetation. Their source material was finaly dispersed silicate particles transported from dry land. The structure and properties of toasted clays are explained by the precipitation of kaolinite as colloidal clumps in which crystallization occurred with formation of intimate intergrowths and variously oriented segregations.
Subsurface samples of shales ranging in age from Pleistocene to Eocene obtained from five Gulf Coast oil wells were examined mineralogically and chemically to determine the nature and extent of burial diagenesis in pelitic sediments. Illite/montmorillonite dominates the mineralogy and undergoes a monotonic decrease in expandability from about 80 to a limit of 20 per cent montmorillonite layers with increasing depth. The interstratification changes from random to ordered at about 35 per cent expanded layers. Discrete illite and kaolinite phases are ubiquitous and judged detrital. The discrete illite (mica) content of the whole rock decreases with depth, while the kaolinite shows no systematic variation. Chlorite occurs in appreciable amounts in only one well and there only in samples from the shallow water facies. This chlorite is also considered detrital.
Whole rock chemical analyses show no systematic variation with depth except for a decrease in calcium and magnesium caused by solution of carbonate. In contrast, potassium increases progressively with depth in the clay-size fraction, indicating a redistribution of potassium within the rock. Detrital illite (mica) seems to break down with increasing depth, thereby supplying potassium for interlayer fixation in illite/montmorillonite as the proportion of illite layers increases. The diagenetic reaction is independent of the geologic age of the sediments and of stratigraphic boundaries. Temperature seems to be more important than pressure in governing the reaction.
The chemical and mineralogical properties of six soils previously believed to be developed from coastal plain sediments were found to be significantly influenced by thin loess overlays and admixtures. The study included two profiles each of the Atwood, Lucedale and Savannah series. Atwood formed primarily in deep loess over coastal plain sediments, Lucedale showed definite loess influence to a depth of 10 in. and possible mixing to a greater depth, whereas the Savannah indicated the presence of slight loess to a depth of 20 in. Both the Atwood and Lucedale soils are well drained, whereas Savannah is moderately well drained and contains a fragipan.
The mineralogy of the coarse clay (2-0·2 μm) appeared to be the most diagnostic feature indicating genetic differences among the soils. Montmorillonite in this clay fraction was most abundant in Atwood, diminished in Lucedale and occurred only in trace amounts in Savannah. In both the Atwood and Lucedale soils very little montmorillonite was found at depths of 35 in. where coastal plain influence apparently predominates. Conversely, aluminous vermiculite-chlorite intergrade minerals were least abundant, in Atwood, increased in Lucedale and occurred in greatest amounts in Savannah.
Accompanying these changes in mineralogy were corresponding changes in the chemical properties. Although no consistent differences in Ca and Mg content were found between the Atwood and Lucedale soils, both Atwood and Lucedale were much higher in exchangeable Ca and Mg than Savannah. Soil pH and base saturation increased in the order Savannah, Lucedale and Atwood.
The reaction between the herbicide “Roundup,” (PAH)3G, which is the commercial name of the iso-propylammonium salt of glyphosate (H3G, N-phosphonomethyl glycine), and montmorillonite was studied. The adsorption of the anionic component of Roundup glyphosate anion, G−3, from an ethanol solution is achieved by repeated immersion of the clay film in the alcohol solution followed by drying for 6–12 hr after each immersion. During the adsorption process the surface acidity of the interlayer space must be sufficiently high to protonate the anion. A zwitterion glyphosate is thereby formed in the interlayer space. Association forms are obtained in the interlayer space in which the COOH and the PO3H groups are linked to the exchangeable cations through water bridges. Adsorption of the glyphosate anion from aqueous solution of Roundup occurs when this anion forms a neutrally or positively charged complex with the exchangeable cation. This may occur with Al- and Fe-montmorillonite, when the molar ratio glyphosate:metal is such that a complex with a 1:1 ratio can be formed in the interlayer space. To clarify the reaction mechanism, adsorption of glycine by montmorillonite from ethanol solution was also studied. The associations obtained between glyphosate and exchangeable cations are less variable than those obtained between glycine and exchangeable cations in the interlayer space of montmorillonite. The following species of adsorbed glycine were identified: glycinium cation, zwitterion glycine, glycine complexed with metal cations either as a monodentate or as a bidentate ligand. In the latter case a chelate is formed.
The ammonia electrode serves as the basis of a simple, accurate method for determination of cation exchange capacity of small (ca. 50 mg) samples of clays. The technique is also capable of accurate measurement of CEC values on the order of 0·01 m-equiv/100 g if larger (ca. 500 mg) samples are used. The procedure, which requires saturation of the exchange sites with ammonium as in the usual methods, utilizes the electrode in the determination of ammonia released by treatment of the ammonium clay by strong base. For a Wyoming bentonite, the technique gave a CEC of 86 m-equiv/100 g with an S.D. (four determinations) of 0·83 m-equiv/100 g. Duplicate runs on the same sample by the conventional Kjeldahl method gave results of 86·0 and 85·5 m-equiv/100 g.
The effects of Na-citrate-dithionite (NaCD), ammonium oxalate in the dark (NH4Ox-D), and photolytic reaction under ultraviolet radiation (NH4Ox-P) on the mineralogy of <2-µm fractions of selected soils from Virginia were investigated. The NH4Ox-D treatment removed the smallest amounts of Al (<0.22%) and Fe (<0.50%) from all soils, indicating low levels of noncrystalline material in these materials. From the six soils examined, NH4Ox-P treatment extracted 5–62% more Fe and 12–300% more Al than the NaCD treatment. The NH4Ox-D and NaCD treatments revealed no X-ray diffraction detectable alterations to mineral phases present in <2-µm fractions of these soils. The NH4Ox-P treatment, on the other hand, produced considerable degradation of hydroxy-interlayered vermiculites in these soils, as evidenced by a shift of the 14-Å X-ray diffraction maxima to lower spacings with heat treatment of the sample. The NH4Ox-P treatment removed variable amounts of hydroxy-Al material from the interlayers of 2:1 layer silicates, depending on their stability and degree of development.
In 2010, Turaev introduced knotoids as a variation on knots that replaces the embedding of a circle with the embedding of a closed interval with two endpoints which here we call poles. We define generalised knotoids to allow arbitrarily many poles, intervals and circles, each pole corresponding to any number of interval endpoints, including zero. This theory subsumes a variety of other related topological objects and introduces some particularly interesting new cases. We explore various analogs of knotoid invariants, including height, index polynomials, bracket polynomials and hyperbolicity. We further generalise to knotoidal graphs, which are a natural extension of spatial graphs that allow both poles and vertices.
A study of the thermal transformation of alkylammonium cations adsorbed on the surface of a montmorillonite in various conditions of hydration has been carried out. The experimental conditions were: inert atmosphere, temperatures below 250°C and time periods up to 270 days. The reactions observed are mainly transalkylations, for which a mechanism of acid catalysis is proposed. A high degree of dissociation of the water remaining on the surface of the clay is required and is attained for an optimal, and rather low, water content of the clay.
The immobilization of soluble Cs from spent fuel elements by ion exchange and direct chemical reaction with clay minerals or shales was investigated under hydrothermal conditions. Various clay minerals or shales were reacted with likely Cs sources and water at 300 bars pressure and 100°, 200°, and 300°C for 4, 2, and 1 months, respectively. Pollucite was the principal product, but CsAlSiO4 was also observed, along with unreacted or hydrothermally altered aluminosilicates. From Cs concentrations of the product solutions partition of Cs between liquid and solids was found to vary depending on the Cs source, the clay or shale phase, temperature, and run duration. For example, illite-Cs2MoO4 interactions resulted in 19, 32, and 95% fixation of added Cs at 100°, 200°, and 300°C respectively. Fixation of as much as 97% of the Cs in some solids was observed. In addition to Cs-aluminosilicates, Cs was fixed on cation-exchange sites by interlayer collapse in montmorillonite. Reactions with Cs2MoO4 also produced powellite because Ca was available in the reaction mixture. The U6+ from β-Cs2U2O7 was reduced to form uraninite by sulfide- and/or organic-rich shales. (Cs,Na)2(UO2)(Si2O5)3·4H2O, an analog of weeksite, was produced in reactions with β-Cs2U2O7. The reaction products pollucite and uraninite can immobilize much of the Cs and U from spent fuel elements because Cs in pollucite is extremely difficult to exchange and U in uraninite is insoluble.