Weathering products formed on surfaces of both potassium and plagioclase feldspar (An70), which were continuously leached in a Soxhlet extraction apparatus for 140 days with 7·21 of distilled water per day at a temperature of approximately 78°C, are morphologically identical to natural products developed on potassium feldspars weathered under conditions of good drainage in the humid tropics. The new products, which first appear as tiny bumps on the feldspar surface, start to develop mainly at exposed edges but also at apparently random sites on flat cleavage surfaces. As weathering continues, the bumps grow outward from the feldspar surface to form tapered projections, which then develop into wide-based thin films or sheets. The thin sheets of many projections merge laterally to form one continuous flame-shaped sheet. The sheets formed on potassium feldspars may then roll to form tubes that are inclined at a high angle to the feldspar surface. Etch pits of triangular outline on the artificially weathered potassium feldspars serve as sites for development of continuous, non-rolled, hollow tubes. It is inferred from its morphology that this weathering product is halloysite or its primitive form. The product of naturally weathered potassium feldspars is halloysite · 4H2O.

The flame-shaped films or sheets formed on artificially weathered plagioclase feldspar do not develop into hollow tubes, but instead give rise to a platy mineral that is most probably boehmite. These plates form within the flame-shaped films, and with continued weathering are released as the film deteriorates. There is no indication from this experiment that platy pseudohexagonal kaolinite forms from any of these minerals under the initial stage of weathering.

High resolution imaging by transmission electron microscopy has revealed a mechanism for the weathering of intermediate microcline in a humid, temperate climate. Dissolution of the feldspar begins at the boundary of twinned and untwinned domains and produces circular holes which enlarge to form negative crystals. Amorphous, ring-shaped structures develop, about 25 Å in diameter, within the larger holes. These rings, in turn, crystallize to an arcuate phase having a 10-Å basal spacing and then to crinkled sheets of illite or dehydrated montmorillonite. The 10-Å layer silicate shows an irregular stacking sequence, including 10-,-20-, and 30-Å sequences. Included plagioclase crystals show a similar mechanism of weathering and, moreover, are more intensely weathered.

The effect of Fe oxidation state on the specific surface area, Sm, of nontronite was studied using the <2-µm, Na+-saturated fraction of the SWa-1 and Garfield nontronite reference clays. The reduction of structural Fe3+ in the octahedral sheet of the nontronite decreased Sm as measured by the adsorption of 2-ethoxyethanol (ethylene glycol-monoethyl ether, EGME). The swellability in water of the nontronite also decreased during reduction. The amount of nonexchangeable Na+, on the other hand, increased with increasing Fe2+ content and was highly correlated with EGME adsorption (r = -.985). The relationship between Sm and Fe2+ was attributed to the collapse of partially or fully expanded layers to unexpanded layers.

Redox cycles are common in nature and likely have a profound effect on the behavior of soils and sediments. This study examined a key component of redox cycles in smectites, namely, the reoxidation process, which has received little attention compared to the reduction process. Unaltered (oxidized) and reoxidized ferruginous smectites (nontronites) were compared using infrared and Mössbauer spectroscopies, and thermal gravimetric analysis. The infrared and thermal gravimetric data revealed that the structural OH content of reduced-reoxidized clay is about 15 to 20% less than in the original (oxidized) sample, indicating that the structure remains partially dehydroxylated even after reoxidation. Mössbaner spectra of reoxidized samples consisted of larger quadrupole splitting for Fe(III) doublets than in the unaltered samples, suggesting that the environment of Fe(III) is more distorted after the reduction-reoxidation treatment.

Low-temperature FTIR spectroscopy was used to characterize the v(OH) region of kaolin-group minerals including well ordered to poorly ordered kaolins from Georgia, Brazil, and England, along with samples of discrete dickite and nacrite. Low-temperature FTIR spectra were useful in resolving dickite- and nacrite-like features present in the spectra of kaolins when cooled to <30 K. These features were not resolved at room temperature and only partially resolved at liquid N2 temperature (77 K). The room-temperature and low-temperature positions of the ν(OH) bands of kaolinite, dickite, and nacrite were linearly correlated with the interatomic OH⋯O distances and this relationship served as the basis for polytype/disorder identification. Dickite or dickite-like disorder was found in high Hinckley-Index kaolinite from Keokuk, Iowa, and from Cornwall, England. Dickite- and nacrite-like features were observed in both high- and low-Hinckley-index kaolinite and the amounts of these stacking sequences generally increased with decreasing Hinckley Index.

The adsorption of Ni(II) and Cu(II) on to the clay minerMs kaolinite, chlorite, and illite has been investigated. The quantity of Ni(II) at pH 6 and Cu(II) at pH 5 adsorbed has been found to vary in the manner chlorite > illite > kaolinite. Examination of the mode of bonding of the metal ions to the clay minerals using X-ray photoelectron spectroscopy (XPS) has been carried out. Comparison of the binding energies for metal ions in octahedral sites in selected minerals (reference minerals) and in simple nickel and copper containing compounds with values for Ni(II) and Cu(II) adsorbed on chlorite indicate that nickel(II) is probably bound as the aquo ion while copper(II) may be adsorbed as Cu(OH)+.

While studying the retention of additives used in tertiary recovery of petroleum (waterflooding) on minerals present in a rock reservoir, an investigation has been undertaken into the adsorption mechanism of Polyacrylamides on to clays. The adsorption of amides and Polyacrylamides takes place exclusively on the external surfaces of the clay particles. The organic molecules are protonated on the surface and adsorbed by ionic forces. There is a linear relationship between the adsorption ratio and the polarizing power of the exchangeable cations of the clay mineral. The adsorption isotherms and the thermal analyses reveal the existence of two adsorption mechanisms: (i) a strong, irreversible adsorption, which corresponds to the formation of a monolayer of chemisorbed molecules, (ii) a more important adsorption of molecules retained by hydrogen bonding, which can be eliminated by heating at low temperature. The retention ratio in the irreversible process, which is practically identical both for acetamide and Polyacrylamide, is low (3 mg/g). It depends on the external cation exchange capacity (CEC) of the mineral and increases with the surface area. The Polyacrylamide adsorption depends on the physico-chemical characteristics of the macromolecule, more particularly on the CONH2/COO−ratio, which determines the extent of the carbon chain, and the molecular weight. The accessibility of the organic macromolecule to the clay particle is controlled by the preceding factors. The quantity of Polyacrylamide irreversibly adsorbed by clay minerals is important in the context of the use of the polymer on a petroleum field. It may be reduced to a minimum by working at low concentrations with a weakly hydrolyzed Polyacrylamide solution.

Many soils developed from volcanic rocks in southern Brazil exhibit spontaneous magnetization caused by the presence of fine-grained maghemite (γ-Fe2O3), but few attempts were made to quantify or characterize this important soil component. To that end, clays were separated from freely drained soils derived from acid (≥63% SiO2), intermediate (54–62% SiO2), and basic (≤53% SiO2) igneous rocks produced by the Paraná flood volcanism. The sample set included soils with a wide range of pedogenic development on different landscape positions. The Fe oxide mineralogy of these samples was examined by using a combination of selective dissolution, magnetic susceptibility, and X-ray diffraction (XRD) techniques. Hematite and maghemite were the primary Fe oxides in mature soils (Oxisols, Ultisols, and Alfisols) developed from basic rocks; whereas goethite was dominant in all other soils, especially those formed from acid-intermediate rocks. The association of maghemite with basic rock materials suggests that it was primarily formed by oxidation of lithogenic magnetite. A strong, positive correlation (R2 = 0.89) was obtained between mass specific magnetic susceptibility (χ) of the clay fractions and maghemite contents estimated by XRD. Either method could be used for quantitative analyses, but χ was more sensitive than XRD at low maghemite concentrations (<2 wt. %). The clay-sized maghem-ites were superparamagnetic with an estimated value for the mass specific magnetic susceptibility (χlf) value of 91,000 × 10−8 m3 kg−1 and frequency dependent variations of 10–15%. The maghemites also had low unit cell constants, which, if attributed entirely to replacement of Fe by Al, would correlate with Al substitutions in the range of 5–16 mole %. Selective dissolution of the soil maghemites was achieved by treatment of Fe oxide concentrates with 1.8 M H2SO4 at 75°C for 2 h.

The factors. (1) possible violations of Darcy’s law. (2) electrokinetic coupling. (3) high viscosity. (4) tortuous flow paths, an. (5) unequal pore sizes have been suggested as possible explanations for the differences between hydraulic flow rates in liquid-saturated clays and sands. The effects of these factors on hydraulic flow rates through saturated clays were investigated.

Hydraulic flow rates, electrical conductivities, and streaming potentials were measured on natural, sodium, and calcium samples of kaolinite, illite and Boston blue clay. Data were taken after increments of one-dimensional consolidation and rebound over the pressure range from one-sixteenth to 256 atm.

The influences of electrokinetic coupling on the hydraulic flow rates were calculated from irreversible thermodynamic relationships together with the hydraulic and electrical data. The other factors were studied by examining the extent to which each factor explains the discrepancies between measured flow rates and those predicted from Darcy’s law and the Kozeny-Carman equation.

The results show that. (1) the possible violations of Darcy’s law and electrokinetic coupling are insignificant. (2) high viscosity and/or tortuous flow paths fail completely to account for the discrepancies between measured and predicted flow rates in clays, an. (3) unequal pore sizes can explain all the discrepancies.

Pierre shale samples from a thin stratigraphic zone within the contact aureole of the lamprophyric Waisen dike record changes due to thermal effects that are not influenced by detrital differences. Analyses of fixed-NH4, mineralogy, and Rock-Eval pyrolysis indicators of organic matter maturity provide new insights on the fixation process. Fixed-NH4 increases with the quantity of authigenic illite formed from illite/smectite, but the maximum fixation per unit of illite formed occurs within the “oil window” where thermal breakdown of organic matter is rapid. Extrapolation of these results to the burial diagenetic regime supports the potential use of fixed-NH4 as an indicator of organic maturity and hydrocarbon migration pathways.

Structural Fe in ferruginous smectite (sample SWa-1, Source Clays Repository of the Clay Minerals Society) was reduced by a mixture of five Pseudomonas species of bacteria in a defined Fe-free medium to determine the effect of microbial reduction on clay swelling. Iron(II), total Fe, and gravimetric water content (mw/mc) were determined in clay gels equilibrated at applied pressures of 0.1, 0.3, and 0.5 MPa. The water content of microbially reduced SWa-1 decreased at all three applied pressures as the Fe(II) content approached about 0.8 mmol Fe(II)/g-clay. As Fe(II) increased from 0.8 mmol/g-clay, however, further change in mw/mc was negligible. Concurrent with microbial reduction of structural Fe was a significant decrease in the swelling pressure (PI) of SWa-1: for example, when mw/mc = 1.2 (g/g), PI changed from 0.47 MPa at Fe(II) = 0.2, to 0.19 MPa at Fe(II) = 0.9 mmol/g-clay. Both biologically and chemically reduced smectites displayed lower values of mw/mc and a concurrent decrease in II as Fe(II) content increased, but the effect of Fe(II) on mw/mc was greater for the microbially reduced smectites at all applied pressures.

The binding of tris-bipyridyl metal complexes of the type M(bp)32+ (M = Fe2+, Cu2+, Ru2+) to hectorite surfaces is shown to occur by two mechanisms. (1) replacement of Na+ ions in the native mineral by cation exchange up to its cation exchange capacity and (2) intersalation of excess salt beyond the exchange capacity. In the cation exchange mechanism, the binding of metal complex is strongly favored over Na+. The intersalation reactions are dependent on the nature of the counter-anion: SO42-, Br- > CIO4−, Cl−. The homoionic M(bp)32+-hectorites, which exhibit rational 18 Å X-ray reflections, have been characterized with regard to their BET surface areas, water adsorption isotherms, types of water present, selected reactions in the intercalated state, and orientation of the complex ions in the interlayer regions. Mixed Fe(bp)32+, Na+-hectorites have also been examined and the results suggest segregation of the two ions between interlayers or within interlayers. Solid state intersalated phases have been isolated with 18 Å and 29.5 Å spacings. In general, surface areas of the intersalated phases are low, but the 18 Å phase derived from [Fe(bp)3]SO4 adsorption shows a high surface area, which even exceeds the surface area of homoionic Fe(bp)32+-hectorite.

The unit-cell characteristics and structures of sepiolite, ferri-sepiolites (xylotile, mountain wood, gunnbjarnite), loughlinite and palygorskite (attapulgite) and their structural relationships are discussed. The chemical, morphological and thermal properties are explained by their structures. The unit-cell characteristics and structures of sepiolite “anhydride”, loughlinite “anhydride” and palygorskite “anhydride” are given. Under low water vapor pressure the phase transformations sepiolite to sepiolite “anhydride” and palygorskite to palygorskite “anhydride” are reversible. It was not possible to synthesize sepiolite in the system MgO−SiO2−H2O under confined pressure within a range of 80° to 300°C

The possibility of the application of sepiolite and related compounds in industry, specially in the automobile industry, is referred to.

Hydrothermal syntheses were performed at various pH values and temperatures to induce variability in kaolinite defect density. Temperature of synthesis ranged from 200 to 240°C, for 21 d. Initial pH at room temperature ranged from 0.5 to 14. The starting material was a hydrothermally treated gel, with an atomic Si/Al ratio of 0.93, partly transformed into kaolinite.

Kaolinite was obtained for a wide range of pH. Although no influence of temperature on “crystallinity” (i.e., defect density) was observed, the effect of pH was important. A continuous series was obtained from a low-defect kaolinite, with high thermal stability and a hexagonal morphology for the most acidic final pH, to a high-defect kaolinite, with low thermal stability and lath shape for the most basic final pH. These variations of kaolinite properties appear related to the pH dependence of kaolinite surface speciation. Increasing pH value results in increased cation adsorption on the kaolinite external surfaces and increases in the elongation of particles.

The different types of iron oxide phases associated with the surfaces of two suites of kaolins from Georgia, U.S.A., and from the Southwest Peninsula of England, have been identified using electron spin resonance (ESR) spectroscopy combined with magnetic-filtration, thermal, and chemical treatments. It has been shown that the English kaolins are coated with a lepidocrocitelike phase, which is readily removed by de Endredy's method of deferrification, while the Georgia kaolins are coated with a hematite- or goethitelike phase, which is not removed by this treatment. Throughout the course of this study, the effects of the various physical and chemical treatments on the brightness values of the kaolins were examined.

The absorption of biologically important purines, pyrimidines, and nucleosides by Li-, Na-, Mg-, and Ca-montmorillonite has been studied in aqueous solutions over a range of pH values 2–12. The initial organic concentrations were about 1 m.molar. The ratio clay to organic compounds was such that only up to 25 per cent of the exchange capacity could be saturated by organic cations, but, depending on conditions, up to 100 per cent of the available organic material was absorbed. Of the nineteen compounds studied, only thymine, uracil, and their nucleosides were not absorbed under the experimental conditions. Absorption occurs primarily as a cation exchange reaction under acid conditions and varies with the basicity of the compounds, their aromatic or non-aromatic character, and the possible extent of their van der Waals interaction with the silicate layers. Nucleosides generally are less strongly absorbed than their purines or pyrimidines because their non-planar structure permits less van der Waals interaction; their absorption is influenced by the differences in swelling behavior of montmorillonite with mono- and divalent cations.

Biotite in deeply weathered granitic rocks in southwestern Australia has altered to exfoliated grains composed of biotite, mixed-layer clay minerals, kaolinite, vermiculite, gibbsite, goethite, and hematite. Discrete vermiculite and vermiculite-dominant mixed-layer clay minerals are not major weathering products. Oxidation of octahedral iron in biotite is associated with ejection of octahedral cations, loss of interlayer K, and a contraction of the b-dimension of the biotite sheet. Si, Mg, Ca, Mn, K, and Na are lost from biotite during weathering, and Ti, Al, Ni, and Cr are retained. Fe and water have been added to the grains during weathering. Much Fe occurs as aggregates of microcystalline, aluminum-rich goethite particles on flake surfaces and within etchpits, with smaller amounts occurring as hexagonal arrangements of lath-shaped crystals of goethite on flake surfaces.

Synthetic hectorite clay minerals were hydrothermally crystallized with direct incorporation of a series of five water-soluble polyvinyl alcohols (PVA) of molecular weights from 9000-146,000. The molecular weight of PVA had little effect on the success of hydrothermal hectorite synthesis, d-spacing or the amount of polymer incorporated. The basal spacings range from 19.5 Å to 20.8 Å and the amount of polymer incorporated ranges from 20 wt.% to 23 wt.%. Incorporation of PVA within the clay inter-layers, along with Li(I) ions to compensate the lattice charge, is indicated. Thermal gravimetric analysis and small angle neutron scattering were used to further examine the polymer-clay systems. Small PVA-clay crystallites that are coated with excess PVA are indicated. Removal of the polymer does not alter the extended synthetic clay network, and the nitrogen BET surface area increases from <5 m2/g to >200 m2/g.

The sequence of mineral reactions involving zeolites and other authigenic phases in tuffaceous sedimentary rocks can be explained by growth- and dissolution-reaction kinetics. Kinetic factors may determine the specific authigenic phases which form and the temporal and spatial constraints on the solution composition during irreversible dissolution and growth reactions in glass-bearing rocks. The glass phase generates a high level of supersaturation with respect to a variety of aluminosilicates in the pore fluid. The sequence of assemblages formed during a series of metastable reactions resembles an Ostwald step sequence. Metastable reactions occur because formation of less stable phases such as gels, clays, and disordered zeolites may lower the total free energy of the glass-bearing system faster than the growth of the stable assemblage including ordered feldspars, quartz, and micas. Eventually, after a series of steps, the most stable silicate assemblage for the bulk composition, temperature, and pressure may form. However, the formation of intermediate metastable phases can delay the attainment of equilibrium by as much as tens of millions of years.

Mössbauer spectra of 15 hematites with Al substitutions between 0 and 10 mole % were taken at room temperature. X-ray powder diffraction indicated dimensions of these hematites in the c-direction to range upwards from 27 nm to crystals large enough to show no line broadening. The Mössbauer spectra showed that magnetic hyperfine fields decreased both with increasing Al-for-Fe substitution and with decreasing crystal size. These relationships indicate that hyperfine field variations cannot, as has been done in the past, be unequivocally related to Al substitution alone. Hyperfine field reductions were paralleled by Mössbauer line broadening due to hyperfine field distributions. Only the hematites heated to 1000°C showed a significant variation of quadrupole splittings with Al substitution. No dependence of quadrupole splitting on crystal size was observed, indicating no detectable distortion of coordination polyhedra in the particle size range studied.