Three authigenic muscovite morphologies are associated with Norphlet Formation stylolitization observed in the Texaco Mobile Area Block 872 #1 well: l)large crystals of 1M muscovite, which grew in the stylolites with their c-axes parallel to the plane of maximum compressive stress; 2) fine-grained bundles of muscovite that occur as pore-fillings near stylolites; and 3) pods of fine-grained muscovite that exist within stylolite insoluble residue and that were precipitated as pore-filling muscovite before the host sandstone pressolved.

The population of large crystals of 1M muscovite grew at 51 ± 9 Ma, pore-filling muscovites precipitated at 77 ± 22 Ma, and muscovite pods have ages of 86 ± 16 Ma, as indicated by 40Ar/39Ar laser fusion. Apparent ages indicate that stylolitization was coincident with the beginning of organic maturation Zone 5 and could be the product of reservoir fluid pressure fluctuations induced by gas leakage. The lower Smackover Formation source/seal rock, acting as a pressure relief valve, could have been compromised by microfractures occurring during hydrocarbon generation and expulsion. Decreases in reservoir fluid pressure would have acted upon the sandstone framework by increasing the effective overburden pressure, thus making the rock more susceptible to pressure solution.

Stylolite frequency and quartz cement volume increase in the finer grained portion of the conventional core. Quartz cement volume correlates inversely to percent sandstone porosity. Apparent muscovite ages indicate that stylolitization occurred after hydrocarbon migration. Silica mobility was limited because pressure solution mineral products were precipitated from within grain films of irreducible water within the sandstone.

Stylolitization of quartz grains accounts for a minimum of 34% of the quartz cement in the upper cored section of the Norphlet Formation and minimum of 17% of the quartz cement in the lower cored Norphlet Formation. Quartz cement volumes are based on stylolite insoluble residue thickness and weight measurements of pyrobitumen within and nearby the insoluble residue seams. Stylolitization of K-feldspar and precipitation of muscovite can release additional silica which may have precipitated as quartz cement.

A dispersion-centrifugation-decantation procedure was used to isolate various particle size fractions from a sample of clay (<2 µm fraction) separated by sedimentation from the Ap horizon of a Webster soil (fine-loamy, mixed, mesic Typic Haplaquoll). The 0.02–0.06 µm size fraction was found to be enriched in an illitic phase associated with randomly interstratified smectite/illite. X-ray powder diffraction, chemical analysis, and high-resolution transmission electron microscopy confirmed that most of the illitic material in the 0.02–0.06 µm size fraction was composed of two-layer elementary illite particles with a layer charge of −0.47 per formula unit. The results demonstrate that this low-charge illitic phase can be physically separated from soil materials and that the low-charge illitic phase has chemical, morphological, and mineralogical properties that are uniquely different from those of smectite and illite.

The interaction of H+- and Cu2+-ions with Ca-montmorillonite was investigated in 0.1 mol/dm3 solutions of Ca(CIO4)2 at 298.2 K by Potentiometrie titrations using both glass electrodes (for H+) and ion specific electrodes (for Cu2+ ). The experimental data were interpreted on the basis of the surface complexation model. The calculations were performed with the least-squares program FITEQL (Westall, 1982) using the constant capacitance approximation. The best fit was obtained with a set of equilibria of the general form

$\begin{array}{c}p{H}^{+}+qC{u}^{2+}+\equiv SOH\iff \left(H^{+}{)}_p\right(C{u}^{2+}{)}_q(\equiv SOH{)}^{(p+2q)+}\\ {\beta }_{p,q\left(int\right)}^s=\frac{\text{[}{H}_{p}C{u}_q(\equiv SOH{)}^{(p+2q)}]}{\text{[}{H}^{+}{]}^p\left[C{u}^{2+}{]}^q\right[\equiv SOH]}\end{array}$

$\equiv TOH-H^{+}\iff \equiv {TO}^{-}log{\beta }_{-1,0\left(int\right)}^S=-5.77(\pm 0.07).$

The full structure of dickite from St. Claire, Pennsylvania, including hydrogen atoms, was refined in space group Cc using time-of-flight neutron powder diffraction data obtained at 12 K and Rietveld refinement/difference-Fourier methods (Rwp = 2.62%, reduced χ2 = 1.915, 113 variables, a = 5.1474(6)Å, b = 8.9386(10)Å, c = 14.390(2)Å, and ß = 96.483(1)°). The non-hydrogen structure is essentially identical to published structures for dickite, but the hydrogen positions are distinct. The inner hydroxyl group is approximately parallel to the (001) plane, inclined by 1.3° towards the tetrahedral sheet. Contrary to published low-temperature infrared (IR) spectra, there is no evidence that dickite possess lower symmetry at low temperatures although there is tentative evidence for statistical occupancy of H3 on more than one site. Low-temperature IR spectra of St. Claire and Wisconsin dickites do not show evidence for more than four hydroxyl groups and are consistent with the reported structure. Upon cooling from 300 to 15 K, the position of the OH3 stretching band increased from 3710 to 3731 cm−1. This large, positive shift in frequency was attributed to the increase in the internuclear O-H3 ⋯ O distance upon cooling. The frequency of the 3655 cm−1 band initially decreased by 2 cm−1 to 3653 cm−1 upon cooling from 300–125 K; however, the band increased in frequency by 1 cm−1 upon further cooling to 15 K. This unusual change in frequency upon cooling is consistent with the assignment of this band to OH2 and OH4. The position of the OH1 stretching band decreased from 3622 to 3620 cm−1 upon cooling, which was attributed, in part, to the observed increase in the Al-O(H1)-Al angle at low temperature.

This paper describes structural models of four pyrophyllite edge faces: {010}, {110}, {100}, and {130}. Water molecules chemisorbed to Lewis acid sites stabilize edge faces both crystallochemically and electrostatically. The detailed assignment of protons to surface oxygens and the orientation of OH bond-vectors both influence the surface Coulomb energy.

The geometry chosen for the electrostatic calculations was infinite pyrophyllite ribbon the thickness of a single phyllosilicate layer and the width of 50 to 70 unit cells. Such a phyllosilicate ribbon has only two edges, a top and bottom, which were simulated using the edge-face models mentioned above. About 94% of the surface Coulomb energy is confined to the edge-face repeat unit. The surface Coulomb energies of the four edge faces are on the order of 2–3 nJ/m, varying ± 1 nJ/m with proton assignment. The Coulomb potential, measured either within the layer or parallel to the layer, has a distinct negative trend near the edge face that can be traced to chemisorbed water molecules. Finally, the correlation between proton Coulomb potentials at the edge face and the coordination environment of the protons is poor, obscured by long-range interactions.

Solutions containing hydroxy-FeAl oligocations (HFA) were prepared by two procedures: (1) treatment of a mixture of FeCl3 and AlCl3 with aqueous Na2CO3, followed by aging of the product and (2) preliminary preparation and aging of hydroxy-Al13 oligocations followed by reaction of the latter with aqueous FeCl3. Ion-exchange of Na-montmorillonite with HFA yield pillared clay (designated as FeAl-PILC) with d(001) values of 1.98–1.56 nm and a surface area of 230 m2/g. The pillar structure, thermal stability, surface acidity, and reduction behavior of the pillared clays were determined by 27Al-NMR, XRD, DTA, Mössbauer spectroscopy, Py-IR, TPD, TPR. Fe/Al ratios greatly affect the pillar structure, surface area and thermal stability of FeAl-PILC. The pillar in FeAl-PILC with Fe/Al ratio <0.5 has a Keggin structure, similar to that of Al-PILC, but the pillar structures of FeAl-PILC with Fe/Al ≥0.5 are the ferric tripolymer species similar to those of Fe-PILC. The basal spacings, surface area, and thermal stability are decreased with increasing Fe/Al ratio. There is relatively strong interaction between Fe and Al in the pillars. The interaction is enhanced with decreasing Fe/Al ratio. Reduction of the Fe phase in FeAl-PILC was reduced by the interaction of Fe with Al.

Refluxing chromium (III) acetate with a Na+-montmorillonite suspension gives rise to the intercalation of linear Cr(III) polyhydroxo-acetate oligomers. Thermally stable chromia pillared mont-morillonite materials are obtained upon calcination under ammonia up to 625°C, and basal expansions up to 6 Å are maintained. The porous materials retain high surface areas (366–464 m2 g−1), a micropore volume of 0.1 cm3 g−1 and narrow pore size distributions centered between 7.5 and 12 Å. The most thermally stable materials in air were those prepared under ammonia at 625°C, containing NH4+ as the exchangeable ion.

The adsorption of the herbicide dimepiperate S-(α;α-dimethylbenzyl)-1-piperidinecarbothioate on homoionic Fe3+-, Al3+-, Ca2+-, and Na+-montmorillonite was studied in aqueous medium. The adsorption is described well by the Freundlich equation. The adsorption capacity decreases in the order Fe3+ > Al3+ > Ca2+ > Na+ clay. The dimepiperate adsorption from chloroform solution was also investigated by analytical, spectroscopic, and X-ray powder diffraction techniques. IR results suggest that the adsorption involves the interaction of the thioester carbonyl group of dimepiperate possibly with the surrounding water of metal ions. On Al3+ and Fe3+ clays, this interaction leads to hydrolysis of the thioester bond and formation of the thiol and carbamic acid derivatives that yield α-methylstyrene and piperidine, respectively.

During processing of Athabasca oil sands, the finely divided solids form an aqueous suspension, which ultimately stabilizes as a gel-like structure retaining up to 90% of the process water. This gelling phenomenon is believed to be caused by colloidal inorganic components. Kaolinite and mica are the main crystalline minerals in these colloidal solids; swelling clays are present in only trace amounts. Non-crystalline components are more concentrated in the finer fraction of the solids. Although the surfaces of the colloidal solids are virtually free of Fe, some contamination with polar organic matter is observed.

Water vapor adsorption isotherms were measured for samples of loessial soil clays modified by removing organic matter and Fe and Al compounds. The isotherms were analyzed by the exponential adsorption isotherm equation. The distribution functions of adsorption energy, average adsorption energies, and surface areas were evaluated simultaneously. The surface areas were the highest for samples after organic matter removal and the lowest when all considered components were removed. Values of the average adsorption energies decreased consecutively after each of the subsequent removal steps while the energy distributions became narrower, indicating in general less variety in surface adsorbing centers.

More than 40 samples of Al precipitation products formed in the presence of organic (aspartic, oxalic, citric, tartaric, malic, salicylic, and tannic acid, and acetylacetone) and inorganic (chloride, sulfate and phosphate) ligands, which were short-range-ordered materials after 2–5 months of aging, were analyzed by X-ray diffraction (XRD), infrared spectroscopy (IR), and transmission electron microscopic (TEM) examination after prolonged periods of aging in the mother liquids (from 7–15 years). Noncrystalline materials were found after 7–10 years of aging in samples formed in the presence of citrate, tartrate, and tannate at pH ≤ 8.0 and at ligand/Al molar ratios (R) ranging from 0.05–0.1; they were found as well in the presence of phosphate and malate at ligand/Al molar ratios from 0.1–0.5. Poorly crystalline Al-oxyhydroxides (pseudoboehmite) without Al(OH)3 polymorphs were found in solutions with a wide range of pH (from 6.0–11.0) in the presence of tartrate, citrate, tannate, malate, salicylate, sulfate, and phosphate after 7–15 years. The crystallinity of these samples was indeed very poor. On the contrary, gibbsite formation was observed in samples formed at pH 7.0 or 8.0 in the presence of oxalate (R = 0.1 or 1.0), aspartate (R = 0.1 and 0.5), malate (R = 0.03 or 0.17), salicylate (R = 0.05), and in samples containing very high concentrations of chloride (R = 700 or 1000). Finally, the formation of gibbsite was promoted in the presence of montmorillonite, but some samples at pH ≤ 6.0 in the presence of citrate (R = 0.1), tartrate (R = 0.1), or tannate (R = 0.02 or 0.1) showed after 6 years of aging interstratification of OH-Al species in the interlayers of the clay mineral and complete lack of Al(OH)3 polymorphs.

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.

Batch reactor experiments were performed at 150°C, 175°C, and 200°C to determine the effect of high pH KOH solutions on the mineralogy of the Opalinus shale. In these experiments, the change in solution quench pH at 25°C, solution composition, and mineralogy were monitored as a function of time for up to ≈ 50 days. Runs were performed in 50 ml titanium hydrothermal reactor vessels. Each reactor was charged with 0.5–5.0 grams of the 80–200 mesh size fraction of Opalinus shale, and 25 ml of solution (0.08 and 0.008 m KOH). Under these high pH conditions, the general sequence of reaction products observed is the formation of phillipsite, followed by K-feldspar ± K-rectorite. Phillipsite is a metastable intermediate that eventually transforms to K-feldspar. This sequence of mineral reaction products is very different from that found in the NaOH system.

The porosities of flocs formed from a used drilling mud were determined by measuring sizes and settling speeds of individual flocs. These flocs were produced in a Couette-type flocculator under a variety of combinations of fluid shear and solid concentrations. In the calculation of floc porosities, a floc settling model was employed that can consider the effects of creeping flow through a floc on its settling speed. Results show that floc structure can be well described as a fractal with a fractal dimension of 1.53–1.64 for the floc size range tested. The effects of flocculation conditions, such as fluid shear and solid concentration, on floc porosity and structure were examined. It was found that floc porosity and fractal dimension were not influenced by solid concentration, but they increased as fluid shear decreased. Empirical expressions for the porosity of drilling mud flocs are obtained from both the floc settling model and Stokes’ law. For solid volume fraction in flocs, the relative difference between these two expressions could be as much as 38%. However, the fractal dimensions estimated based on the two settling models are nearly the same.

Mica domains have received less attention in the literature than smectite quasi-crystals. This study was conducted to determine whether mica crystals form domains in suspension, the conditions in which those domains exist, and the distribution of adsorbed Na and Ca ions in the domains. Particle size distributions and electrophoretic mobilities (EM) of Silver Hill illite in suspension densities of 0.5 g liter−1 were determined by photon correlation spectroscopy (PCS). Solutions at salt concentration from 2 to 10 mmolc liter−1, sodium adsorption ratio (SAR) from 0 to ∞ (mmol liter−1)0.5, and pH values 5, 7, and 9 were used to prepare the clay suspensions. The particle size of Silver Hill illite suspensions showed a bimodal distribution. Through PCS measurements at low angles, the second peak of the bimodal distribution of the illite was found to be associated with the rotational movement of the b-dimension of the particles. Illite domains broke down in the range of SAR 10 to 15 (mmol liter−1)0.5 equivalent to exchangeable sodium percentages (ESP) of 13 to 18. Illite thus demonstrates a similar stability to smectites that require ESP ≈ 15 to disaggregate quasi-crystals. The EM of the illite particles increased drastically when the SAR increased from 2 to 10 (mmol liter−1)0.5. This increase in EM could not be explained exclusively by the change in the particle size. Cation demixing is required to explain the increase of the zeta potential at the shear plane. The EM of the Silver Hill illite was doubled when the pH increased from 5 to 9 at SAR > 15, but no pH effect was found when SAR < 15. The effect of pH on the EM at SAR values > 15 can be understood if we consider that at SAR > 15 most of the particles are single platelets. The relative importance of variable charge on single platelets or crystals is apparently greater than on domains because the pH affected the mobility of the individual crystals but not the mobility of the domains. The combination of particle size distribution and EM data gives additional information about the zero point of charge of the variable charge, also called point of zero net proton charge (PZNPC) of the clay. For Silver Hill illite, we estimate a PZNPC value between 5 and 7.

Structural and diffraction criteria for distinguishing between t-1M, c-1M, m-1M, and 3T illite varieties are described. The t-1M illite corresponds to a one-layer monoclinic structure with vacant transsites. The c-1M illite has vacant cis-octahedra forming one of two symmetrically independent point systems; the other cis-octahedra as well as the trans-octahedra are occupied; and the m-1M illite corresponds to the structure in which cations are statistically distributed over available trans- and cis-sites. For t-1M, c-1M, and m-1M, the values of |c cos β/a| are equal to 0.39–0.41, 0.29–0.31, and 0.333, respectively. Application of these criteria demonstrates that illite samples described in the literature as the 3T polytype usually are c-1M instead. The relatively common occurrence of c-1M illite in association with t-1M and 2M1 polytypes has been recognized in illite from hydrothermal alterations around uranium deposits located in the Athabasca basement (Saskatchewan, Canada). The c-1M illite from these deposits was previously described as 3T one.