A new appraisal of radiation-induced defects (RID) in natural kaolinite, i.e., positive trapped holes on oxygen atoms, has been undertaken using Q-band EPR spectra, recorded at 93 K, of irradiated annealed and oriented kaolinite samples originating from various environments. Three different centers were identified. Two of the centers, A- and A’-centers, are trapped holes on oxygen from Si-O bonds. They have a distinct signature and orthogonal orientation, i.e., perpendicular and parallel to the (ab) plane, respectively. The third center, the B-center, is a hole trapped on the oxygen bonding Al in adjacent octahedral positions (AlVI-O−-AlVI bridge). This confirmed some previous assignments from the literature, some others are no longer considered as valid.

A least squares fitting procedure is proposed to assess the RID concentration in any kaolinite. It allows a quantitative approach of the thermal stability of RID. Isochronal annealing shows that the thermal stability of the centers decreases in the order A, A′, B over the temperature range 0–450°C: (1) B-center is completely annealed above 300°C; (2) A′-center can be annealed by heating at 400°C for more than two hours; (3) A-center is stable up to 450°C. The activation energy and the magnitude of the mean half-life for A-center is evaluated through isothermal annealing at 350, 375 and 400°C, with Ea = 2.0 eV ± 0.2, and t½ > 1012 years at 300 K. The stability of A-center seems to decrease with increasing crystalline disorder. Nevertheless, it is high enough for radiation dosimetry using kaolinites from any environment on the Earth's surface.

The sorption properties of carbon-composite materials based on montmorillonite and hydrotalcite matrices have been studied using nitrogen adsorption isotherms and inverse gas chromatography. Carbon composite materials derived from both types of inorganic precursors contain pore structure accessible for adsorbate molecules. Adsorption capacity per unit mass of these composite adsorbents is larger in the case of hydrotalcite than in montmorillonite-based materials. Exposing these materials to ambient conditions results in their hydration. Subsequent water removal by heating under vacuum increases nitrogen adsorption capacity, which is explained by the opening of the adsorption space. The water content of hydrated samples and its effect on adsorption capacity is greater for the case of hydrotalcite-based materials. No direct relationship between carbon content and adsorption properties of the materials studied is observed.

Suspensions were produced by mixing Na-saturated, Upton montmorillonite with aqueous solutions containing different concentrations of 1,4-dioxane. Each suspension was deposited on a porous ceramic filter in an environmental chamber, and the solution was expressed from it by admitting gaseous helium to the chamber at a slightly elevated pressure. The chamber was fitted 1) with beryllium windows so that X-rays could be transmitted into and out of it and 2) with a drain so that the expressed solution could be conducted to the outside atmosphere. Once a filter cake had formed on the filter, the pressure of the gaseous helium was raised in successive increments and, after each increment, the c-axis layer spacing(s) was determined by X-ray diffraction. Increasing the concentration of 1,4-dioxane caused some of the fully expanded layers to collapse to the partially expanded state (c-axis spacing = 15 Å) and appeared to cause the remaining fully expanded layers to move farther apart, especially at the higher pressures. Alternative explanations were given for these apparently contradictory results.

Infrared spectroscopy is used to distinguish between octahedral and tetrahedral substitutions in an interstratified illite-smectite clay. The Hofmann-Klemen (Li) test suggests that the AlMg□ and FeMg□ octahedral vacancies are preferentially occupied by Li after thermal treatment at 250°C. The ammonium (Chourabi-Fripiat) test reveals the beidellitic character by the formation of two OH stretching modes upon deammonation. The illitic layers are not affected since K is not exchangeable.

Two orientations of white micas with subordinate chlorite have been observed in a fine-grained (50 Å to 2 μm) matrix of a Silurian lower anchizonal mudrock from central Wales: one parallel to bedding and one parallel to cleavage that is approximately 30°-50° to bedding. Bedding-parallel micas consist of small (50-200 Å thick) deformed packets (1Md polytype) and larger (100 Å-2 μm) strain-free grains (2M1 polytype). All strained micas and some strain-free grains have compositions varying from Mu86Pg14 to Mu58Pg42, intermediate to muscovite and paragonite, and falling within the Mu-Pg solvus. Individual packets of layers are chemically homogeneous and some of them give only one set of 00l reflections (d ≈ 19.6 Å). Micas with such intermediate compositions are metastable. Some packets of coarse, strain-free micas have compositions of approximately Mu93Pg7 or Mu11Pg89. Split pairs of 00l reflections with d-values of 20 Å and 19.6 Å, and 20 Å and 19.2 Å, respectively, were observed in some SAED patterns, suggesting coexistence of muscovite and intermediate Na/K mica (∼Mu60Pg40), and of discrete muscovite and paragonite, consistent with the splitting of the basal reflections of micas as observed in bulk-rock XRD patterns. Cleavage-parallel micas (2M1 and 3T polytypes) occur as strain-free large grains (200 Å to 2 μm) of discrete muscovite (Mu100Pg0) and paragonite (Mu6Pg94), often with subhedral to euhedral cross-sections.

The data suggest that bedding-parallel metastable micas with disordered interlayer K and Na were initially derived from alteration of smectite during burial diagenesis. They subsequently underwent dissolution, with crystallization of more evolved bedding-parallel micas during deep burial. Discrete grains of stable muscovite and paragonite then crystallized in the cleavage orientation through tectonic stress-induced dissolution of bedding-parallel matrix micas. Combined XRD and TEM/AEM data further show that the so-called 6:4 ordered mixed-layer paragonite/muscovite actually corresponds to cation-disordered, homogeneous mica of intermediate composition.

A prograde sequence of corrensite and chlorite in pelitic rocks of the diagenetic zone, anchizone, and epizone (illite crystallinity indices = 0.17–0.58°Δ2θ) of the Gaspé Peninsula, Quebec, was studied by analytical and transmission electron microscopy (AEM and TEM). The data collectively suggest that diagenesis/metamorphism of chlorite and corrensite follows a sequence of phase transitions, compositional homogenization, and recrystallization, approaching a state of equilibrium for which chlorite is the stable phase.

Corrensite occurs as coalescing, wavy packets of layers intergrown with chlorite and illite in the diagenetic and low-grade anchizonal rocks. Intergrowths of discrete chlorite and corrensite crystals, interstratified packets of chlorite and corrensite layers, terminations of smectite-like layers by chlorite layers, and 2–3 repeats of R2- and R3-ordered chlorite-smectite mixed layers occur. These materials are alteration products of detrital biotite or other precursor phases like trioctahedral smectite. The crystal size and proportion of corrensite decrease significantly from the diagenetic zone to the anchizone. Deformed corrensite is crosscut by straight packets of chlorite and corrensite in the diagenetic sample. Some chlorite occurs as discrete, euhedral to subhedral crystals intergrown with or enclosed by other phases in the absence of corrensite. The crystal size of chlorite and definition of crystal boundaries increase whereas density of crystal imperfections and randomness in orientation decrease with increase in grade of diagenesis/metamorphism. Crystals that are kinked or bent, or display gliding along (001) form low-angle boundaries with relatively defect-free crystals, implying deformation during crystal growth. Abundant well-defined low-angle boundaries associated with dislocations are observed in the higher grade rocks, consistent with a stage of readjustment of crystal boundaries during crystal growth. The AEM analyses show that the corrensite has lower Fe/(Mg + Fe) and Al/(Si + Al) than the coexisting chlorite in the diagenetic sample, and that the ranges of composition of chlorite of different grades overlap and become smaller with increasing grade, implying prograde homogenization.

The data imply that corrensite is a unique phase that is metastable relative to chlorite: its conversion to chlorite occurred at a grade as low as that of the high-grade diagenetic zone. The textural relations suggest that the metamorphic crystallization and recrystallization were coeval with deformation processes due to tectonism, partially modified by subsequent contact metamorphism. The data, combined with those of previous reports, suggest that the Gaspé Ordovician rocks constitute a part of a regional distribution of trioctahedral phyllosilicate-rich rocks in the northern Appalachians. The regional occurrence of abundant chloritic minerals is thus directly related to a specific tectonic regime with precursor sediments largely derived from an andesitic arc system(s).

In the electrocoagulation process a suspension of kaolinite and bentonite is coagulated by electrochemical treatment where aluminum anodes are dissolved and aluminum ions react with clay particles, forming flocs which precipitate. Several factors affecting the efficiency of electrocoagulation are investigated. They include NaCl concentration, voltage, and flow conditions within the cell. Increased NaCl concentration led to lower electric resistance and cleaner running electrodes. Enhanced shear associated with recirculation resulted in clear supernatant and more compact floes. While increasing the feed rate, which was equivalent to decreasing aluminum concentration through the system, reduced cake height but increased turbidity.

Hectorite and saponite are exchanged with [Al13O4(OH)24(H2O)12]7+ and the amount of Al3+ adsorbed and Na+ released are followed as a function of the exchange conditions. On saponite the reaction is a pure ion exchange with 2–2.15 mmol Al3+/g adsorbed and release of 0.80 mmol Na+/g. On hectorite the ion exchange is accompanied by supplementary hydrolysis-polymerization of Al13. When excess Al is offered in the form of Al13, ion exchange is incomplete and is accompanied by precipitation and polymerization of Al13 on the surface of both hectorite and saponite. The typical spacing of 1.8 nm is developed after washing, when at least 1.3–1.4 mmol Al3+/g is adsorbed. Above a loading of 2.2–2.5 mmol/g the 1.8 nm spacing is obtained without washing. Only pillared saponite with a loading of at least 1.9 mmol Al3+/g is thermally stable up to 550°C.

A very simple technique is proposed for a quantitative or semiquantitative interpretation of X-ray diffraction (XRD) patterns for two-component mixed-layer structures. It is suitable for a determination of the Reichweite (R) values and proportions of component layers from graphical simulations of basal peak positions for mixed-layer structures with definite layer types. This technique can be successfully used for illite-smectites, but the accuracy of the results obtained for other mixed-layer structures is somewhat lower. In addition to the graphical technique, simple linear relationships are proposed for the calculation of layer proportions. Such relationships can be easily obtained for any mixed-layer structure with any R and any thicknesses of interstratified layers.

Structural parameters reported in the literature for mixed-layer illite-smectites, kaolinite-smectites, etc., were used to check the reliability of the method presented. It is concluded that the technique works well and produces parameters that are in agreement with those published.

Dioctahedral tosudite, a regular interstratification of dioctahedral chlorite-dioctahedral smectite, occurs associated with kaolin in the hydrothermal area of Delgado, Neutla, Mexico. Its composition corresponds to the formula:

$$\left( {S{I_{13.77}}A{L_{2.23}}} \right)A{L_8}{O_{40}}{\left( {OH} \right)_8} \cdot C{A_{0.39}}N{A_{0.03}}{K_{1.06}} \cdot \left( {A{L_{3.79}}F{E^{ + 3}}_{0.09}F{E^{ + 2}}_{0.06}M{G_{0.26}}} \right){\left( {OH} \right)_{12}}.$$

Experimental alteration of albite in deionized-distilled water at 150° to 225°C for various times up to 30 days was performed to elucidate formation processes for alteration products of albite in aqueous solution. The alteration products were examined by X-ray powder diffraction, scanning electron microscopy, transmission electron microscopy (TEM), and energy dispersive X-ray analysis (EDX). The surface compositions of albite before and after alteration were investigated by X-ray photoelectron spectroscopy (XPS). TEM clearly showed that an amorphous leached layer was produced on the albite surface at the earliest alteration stage together with small amounts of allophane. The leached layer increased successively in thickness and tended to be detached from the albite surface as alteration proceeded. Noncrystalline fibers less than 0.5 µm in length appeared within the leached layer matrix and transformed into thin flaky smectite and small amounts of K-mica. The leached layer gave electron diffraction patterns with a diffuse halo, whereas the flaky smectite displayed rings at 4.51, 2.61, and 1.54 Å. EDX confirmed that the flaky smectite consisted mainly of Si and Al, and small amounts of Na. The smectite was formed in the stability field of Na-smectite for the system of Na2O-Al2O3-SiO2-H2O.

Recent pedological evidence of the widespread distribution of beidellites in soils indicates the need for a greater knowledge of the effect of charge location on the microstructural organization of Na+ smectite in gels. After equilibration at a suction pressure of 3.2 kPa before and after desiccation, TEM observations showed large differences between a beidellite and both a low and high charge montmorillonite. Monolayers were rare; individual layers were instead organized in particles with larger interparticle distances. This has implication for theories relating swelling pressures to interlayer distances or surface areas and implies the need for a geometrical approach to the study of swelling in smectites. Location of isomorphous substitution in the tetrahedral sheet of smectites results in an increased lateral extension of overlapping layers. This was reflected in a greater capacity to rehydrate after desiccation. Increased number of layers in particles were found with increasing surface charge density. The geometric organization of the particles is critical to the understanding of the ability of Na+ smectite to hold water against an applied suction.

Smectite single crystals of superior quality were synthesized at high pressures and temperatures using a modified belt type high pressure apparatus. Pressure-temperature conditions were established for smectite formation by quenching experiments in the pressure range from 2–5.5 GPa and temperatures of 700°–1000°C. Smectite crystals with extraordinary quality were formed beyond 3 GPa and 1000°C with coexisting phases of coesite, kyanite, jadeite, and in some cases with mica and glass. Smectite was confirmed from the XRD taken after intercalation of ethylene glycol. The smectite crystals were considered to be quenched crystals metastably from the hydrous silicate melts formed at high pressures and temperatures.

Alteration experiments have been performed using RTT7 and synthetic basaltic glasses in MgCl2−CaCl2 salt solution at 190°C. The duration of experiments ranged from 0.25 to 463 days. The alteration products were studied by Scanning Electron Microscope (SEM), Scanning Transmission Electron Microscope (STEM), X-ray diffraction (XRD) and Electron Spectrometry for Chemical Analysis (ESCA). For both glasses, the early alteration product is a hydrotalcite-like compound [Mg6Al2CO3(OH)16·4H2O] in which HPO42−, SO42− and Cl− substitutes for CO32−. The measured basal spacing is 7.68 Å for the hydrotalcite formed from R7T7 glass and 7.62 Å for the hydrotalcite formed from basaltic glass which reflect the high Al/Al + Mg ratios x (0.34 ≤ x ≤ 0.46). The chemical microanalyses show that the hydrotalcite is subsequently covered by a silica-rich gel which evolves into saponite after a few months. These results support the use of basaltic glasses alteration patterns in Mg-rich solution, to understand the long-term behavior of R7T7 nuclear waste glass.

Saponites were hydrothermally grown in the presence of amounts of NH4+, Na+, K+, Rb+, Ca2+, Ba2+, and Ce4+ equivalent with the CEC of the saponite (155 meq/100 g), with or without F−, at a temperature of 200°C for 72 hr. XRD and CEC data revealed the formation of a two-water-layer saponite with mainly Mg2+ as interlayer cation. Dehydration occurred between 25° and 450°C and dehydroxylation occurred in two steps between 450° and 790°C and between 790° and 890°C. The relatively small length of the b-axis between 9.151 and 9.180 Å is explained by considerable octahedral Al substitution (between 0.28 and 0.70 per three sites) and minor tetrahedral Al substitution (between 0.28 and 0.58 per four sites). Under the synthesis conditions applied in this study, less than 13% of the interlayer sites are occupied by Na+, K+, and Rb+; between 13.3% and 21% by Ca2+ and Ba2+; while NH4+ gives the highest value at 34%. The remaining sites are mainly filled by Mg2+. Ce4+ is not found in the saponite structure due to the formation of cerianite, CeO2. The presence of F− had little influence on the saponite composition. The formation of Mg-saponites is explained by a model in which an increased bayerite formation resulting in a higher octahedral Al3+ substitution and more Mg2+ in solution. Mg2+ is preferentially incorporated compared with the other interlayer cations due to its smallest ionic radius in combination with its 2 + charge.

Takovite, Ni6Al2(OH)i6CO3-5H2O, with molar Ni/Al ratios of 2.5 and 3 is prepared by precipitation at pH levels of 7 and 10, periods of reaction of 3 and 20 hr, and calcination temperatures varying between 120° and 8 5 3°C. The quantity of reduced Ni is determined as a function of the calcination temperature, and the solid phases remaining after reduction are determined with XRD. The Ni/Al ratio, pH of precipitation, and calcination temperature are important preparation conditions. A precursor of a Ni/Al ratio of 2.5 precipitated at a pH-level of 10 exhibits on reduction metallic Ni particles of about 15 nm irrespective of the drying or calcination temperature. After reduction, a considerable amount of NaAlO2 is present. Metallic Ni particles of 6 nm are present in a reduced precursor of Ni/Al ratio of 2.5 precipitated at a pH-level of 7. The size of the Ni particles present in a reduced precursor of Ni/Al ratio of 3 precipitated at a pH-level of 10 rises from 4–8 nm to 16 nm after calcination at temperatures increasing from 120° to 853°C. The last precursor contains much less sodium, and shows after reduction a disordered NiO phase containing some alumina. Especially, the takovite with the molar Ni/Al ratio of 2.5, thoroughly washed to remove Na, and calcined at T ≤ 260°C before reduction of Ni provides a promising catalyst for the production of hydrogen-carbon monoxide flows out of methane and steam.

The electrochemical properties of kaolinite before and after modification with chlorodimethyl-octadecylsilane have been studied by electrophoretic mobility, surface charge titration, and extrapolated yield stress measurements as a function of pH and ionic strength. A heteropolar model of kaolinite, which views the particles as having a pH-independent permanent negative charge on the basal planes and a pH-dependent charge on the edges, has been used to model the data. The zeta potential and surface charge titration experimental data have been used simultaneously to calculate acid and ion complexation equilibrium constants using a surface complex model of the oxide-solution interface. The experimental data were modeled following subtraction of the basal plane constant negative charge, describing only the edge electrical double layer properties. Extrapolated yield stress measurements along with the electrochemical data were used to determine the edge isoelectric points for both the unmodified and modified kaolinite and were found to occur at pH values of 5.25 and 6.75, respectively. Acidity and ion complexation constants were calculated for both sets of data before and after surface modification. The acidity constants, pKa1 = 5.0 and pKa2 = 6.0, calculated for unmodified kaolinite, correlate closely with acidity constants determined by oxide studies for acidic sites on alumina and silica, respectively, and were, therefore, assigned to pH-dependent specific chemical surface hydroxyl groups on the edges of kaolinite. The parameters calculated for the modified kaolinite indicate that the silane has reacted with these pH-dependent hydroxyl groups causing both a change in their acidity and a concomitant decrease in their ionization capacity. Infrared data show that the long chain hydrocarbon silane is held by strong bonding to the kaolinite surface as it remains attached after washing with cyclohexane, heating, and dispersion in an aqueous environment.

The composition and origin of vanadium-bearing clay minerals in the Jurassic (Morrison and Entrada Formations) sandstones of the Colorado Plateau are reassessed using microanalyses (microprobe and scanning electron microscope). The main V-clays are authigenic illite and chlorite of various petrologic habits: clay casts and matrix, pore lining, replacement of detrital grains. The chemical composition of the V-clays is similar in three different localities in the Morrison Formation separated by about 50 km, suggesting that the V-clays are the result of a large regional event. In both illite and chlorite, Al and V are inversely correlated, showing that V replaces Al in the octahedral position. The chlorite contains a complex mixture of divalent and trivalent cations that cannot fit within a sudoite structure. A classification of V-micas is proposed that employs V3+/sum of the octahedral cations vs. the sum of the interlayer charges. V-illite and roscoelite from the Colorado Plateau are characteristic of diagenetic/hydrothermal environments. For a given locality the composition of the V-clays does not vary with habit, showing that these minerals formed at thermodynamic equilibrium.

Two-line ferrihydrite is an important adsorbent of many toxics in natural and anthropogenic systems; however, the specific structural sites responsible for the high adsorption capacity are not well understood. A combination of chemical and spectroscopic techniques have been employed in this study to gain further insight into the structural nature of sites at the ferrihydrite surface. The kinetics of iron isotopic exchange demonstrated that there are at least two types of iron sites in ferrihydrite. One population of sites, referred to as labile sites, approached iron isotopic equilibrium within 24 hr in 59Fe-NTA solutions, while the second population of sites, referred to as non-labile, exhibited a much slower rate of isotopic exchange. Adsorbed arsenate reduced the degree of exchange by labile sites, indicating that the anion blocked or greatly inhibited the rate of exchange of these sites. Mössbauer spectra were collected from a variety of samples including 56Fe-ferrihydrite samples with 57Fe in labile sites, samples containing 57Fe throughout the structure, and samples with 57Fe in non-labile sites. The spectra showed characteristic broad doublets signifying poor structural order. Refined fits of the spectra indicated that labile sites have larger quadrupole splitting, hence more local distortion, than non-labile sites. In all cases, the spectra demonstrated some degree of asymmetry, indicating a distribution of Fe environments in ferrihydrite. Overall spectral findings, combined with recent EXAFS results (Waychunas et al., 1993), indicate that labile sites likely are more reactive (with respect to iron isotopic exchange) because they have fewer neighboring Fe octahedra and are therefore bound less strongly to the ferrihydrite structure. The labile population of sites probably is composed of end sites of the dioctahedral chain structure of 2-line ferrihydrite, which is a subset of the entire population of surface sites. Mössbauer spectra of samples containing adsorbed arsenate indicated that the anion may slightly decrease the distortion of labile sites and stabilized the structure as a whole by bidentate bonding.

An X-ray diffraction study of vermiculitized micas in ultramafic and mafic intrusive rocks from Cheongyang, Korea, shows the following weathering sequence: mica → ordered mica/vermiculite interstratification → vermiculite. Electron microprobe analyses show the general trends of K leaching and Ca enrichment with increased weathering. The vermiculitization of phlogopite from ultramafic rocks proceeds by means of a continuous decrease in Al-for-Si tetrahedral substitutions and a progressive increase in Al-for-(Fe2+ + Mg) octahedral substitutions in the early stage of weathering. These substitutions occur to compensate for the excess of negative charge in the mica-like layer, in agreement with currently accepted vermiculitization mechanisms. They change to a slight increase of Al-for-Si tetrahedral substitutions in the late stage of the vermiculitization of phlogopite, owing to the oxidation of Fe despite its low content. However, the behavior of Fe in the late stage of the transformation of biotite into vermiculite is significantly different; that is, Fe increases substantially. The reason for this Fe increase in the late stage remains unresolved. Recalculations of the structural formulas on the basis of several assumptions indicate that the oxidation of Fe is necessary for the vermiculite derived from biotite to form the reasonable structural formulas.