Iron phyllosilicates with 1:1 and 2:1 layer structures were prepared from silicic acid, ferrous sulfate and sodium hydroxide. Hydrothermal treatment at 100–200°C of a reaction mixture with an initial Fe/Si ratio of 1.5 gave the 2:1 iron phyllosilicate, whereas a Fe/Si ratio of 2.25 gave the 1:1 phyllosilicate. The 57Fe Mössbauer spectroscopy showed that 60% of the iron in the 1:1 phyllosilicate is ferrous, versus only 3% in the 2:1 phyllosilicate. The values of quadrupole coupling showed that the iron-oxygen tetrahedra and octahedra in the 2:1 phyllosilicate were more deformed than those in the 1:1 phyllosilicate.

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.

Raman and Fourier-transformed infrared spectra of natural trioctahedral chlorites of polytype IIb were obtained for a series of samples characterized by distinct Fe/(Fe + Mg) and Si/Al ratios ranging, respectively, from 0.04 to 0.94 and from 5.18 to 1.86. All samples were characterized by X-ray powder diffraction, and quantitative electron microprobe analysis. In the 3683-3610-cm−1 spectral range, the wave number of the OH-stretching band from the 2:1 layer (band I) decreased with an increase of iron content at constant Al(IV) content. The more intense bands II and III at about 3600 cm−1 and 3500 cm−1, were assigned to hydroxyl groups involved in hydrogen bonds: (SiSi)O... HO, with the hydrogen bonds being roughly perpendicular to the basal plane, and (SiAl)O... HO, respectively. At higher tetrahedral Al and octahedral Fe contents, spectra exhibited OH-bands II and III, respectively, at a lower frequency. Band III intensity increased and band II was enlarged for chlorites displaying higher Al(IV) contents.

In the 1300–1350-cm−1 spectral range, most infrared spectra displayed intense bands at 1090, 1050, 990, and 960 cm−1, which were assigned to T-O stretching of symmetry species Al and E1. The second type of bands observed both in Raman and infrared spectra were at about 650–800 cm−1; they were assigned to OH vibrations and were strongly dependent on the composition of the interlayer octahedral sheet, especially on the Fe content.

Large-pore La-Al-pillared montmorillonite was prepared by reacting montmorillonite with hydrothermally treated mixtures of aluminum chlorohydrate and lanthanum chloride. The large-pore La-Al-pillared montmorillonite is characterized by basal spacings of about 26 Å, surface areas of 300–500 mVg, and pore volumes in the range 0.2–0.3 cm2/g. Large-pore pillared montmorillonite products were obtained from solutions refluxed for >72 hr or treated in autoclaves at 120°–160°C for 12–96 hr. The most favorable pillaring solution for the production of large-pore La-Al-pillared montmorillonite had an OH/Al ratio of 2.5, a La:Al ratio of 1:5, and was 2.5 M with respect to Al. The elemental composition of large pore La-Al-pillared montmorillonite is similar to that of a conventional Al-pillared montmorillonite that has a basal spacing of about 19 Å. The 26-Å spacing is believed to be associated with the formation of large polymeric La-bearing Al-cations upon hydrothermal treatment of the solutions.

Three gels of illitic composition having different octahedral substitutions were hydrothermally treated in distilled water at 300°C and 500 bars for 7 to 90 days. The gel of the composition K0.7Al2.0(Si3.3Al0.7)O10(OH)2, having no octahedral substitutions, yielded poorly crystalline and randomly interstratified illite/smectite (I/S) having possibly 30% or more expandability. These I/S particles occurred predominantly as foliated or compact lamellar aggregates having morphological features characteristic of common smectite. Laths having a morphology similar to that of diagenetic “fibrous illites” were also found in small amounts after the gel had been aged for 35 days. Their chemical composition was similar to that of the foliated aggregates of I/S in the same run.

Illitic gel having the composition K0.7(Al1.7Fe3+0.3)(Si3.3Al0.7)O10(OH)2 having octahedral Fe3+ substitutions yielded more and better crystalline I/S. The reaction products of the 7-35-day runs consisted mainly of randomly interstratified I/S having an expandability of 90 to 65%. The I/S particles occurred as foliated or compact lamellar aggregates having a smectite-like morphology, as described above. The Fe3+-bearing gel yielded, after 90 days of ageing, an Rl-ordered I/S having 25% expandability and a morphology of ribbons and hexagonal platelets.

Illitic gel of composition K0.8Al1.6Mg0.4)(Si3.6Al0.4)O10(OH)2 having octahedral Mg2+ substitutions produced no illite even after 90 days of ageing, but a pure smectite in the form of foliated aggregates.

The Kimmeridgian-Volgian(-Ryazanian) clay stone is the principal oil source rock in the troughs of the North Sea. Randomly (R0) ordered mixed-layer illite/smectite (I/S) appears to have transformed to R1-(IS) or R3-(ISII) ordered simultaneously with oil generation. The proportion of illite layers in I/S increased to 95% during diagenesis in these claystones. Exceptions are three samples of I/S of probably bentonitic origin; these have apparently changed during diagenesis to R0-ordered I/S containing 40-50% illite layers. Fine fractions of the claystones dominated by I/S were analyzed by 27Al and 29Si magic-angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy, 57Fe Mössbauer spectroscopy, and X-ray powder diffraction (XRD), and for total chemical composition. Si/Al ratios determined from MAS-NMR agree closely with those calculated from total chemical analysis; however, tetrahedral and octahedral Al occupancies were most accurately determined by NMR. An increase in the percentage of illite layers and in the ordering of the I/S was accompanied by fixation of K+ and NH4+ in the I/S, by tetrahedral Al-for-Si substitution, and by octahedral Al-for-(Mg + Fe) substitution, resulting both in an increase of charge in the 2:1 layers and in a migration of charge from octahedral to tetrahedral sheets. The I/S of probably bentonitic origin had a larger tetrahedral and a smaller octahedral charge than expected from its content of illite layers. MAS-NMR showed a significantly higher content of tetrahedral Al (most likely in smectitic sites) than expected from the percentage of illite layers calculated from XRD. Correspondingly, XRD of K+-saturated and glycolated specimens showed that several smectite layers possessed a significant charge. A constant b-dimension of the I/S and the presence of a significant charge in the smectite layers suggest that a transformation of smectite to illite layers in the I/S by tetrahedral Al-for-Si substitution followed by interlayer cation fixation and interlayer contraction is the most probable genesis for the I/S investigated.

To identify the far-infrared (FIR) absorption bands related to K cations in micas, spectra of muscovite, phlogopite, and biotite were compared with the spectra of pyrophyllite and talc, which have no compensating cations, and to the spectra of micas in which K is substituted by mono- and divalent cations. Dichroic experiments using single crystals of these micas showed that some of the bands or components related to K have a strong in-plane and out-of-plane dichroic character. These experimental data led to the assignment of the FIR bands at 110, 91, and 83 cm−1 for muscovite, phlogopite, and biotite, respectively, which have no in-plane and out-of-plane dichroic character, to the vibration of the double ring of oxygen atoms that constitutes the cage in which K is located (mode III).

Bands at 146, 136, and 152 cm−1 for muscovite, phlogopite, and biotite, respectively, which have a strong out-of-plane dichroic character, were assigned to the out-of-plane vibrations of K atoms (mode IV). Some of the components at 190, 158–153, and 145–124 cm−1 for muscovite, phlogopite, and biotite, respectively, which have a strong in-plane dichroic character, are possibly related to the in-plane vibrations of K atoms (modes I and II). The 165-cm−1 band of muscovite is a lattice mode of vibration. Frequencies of modes III and IV of the compensating cations of micas in which K was substituted by mono- and divalent cations exchanged as a function of $\sqrt{Z/m}$ where Z is the charge and m the mass of the cation. Modes III and IV were well resolved and very sensitive to the crystallochemical properties of the structure (di- or trioctahedral character, Fe content, etc.). FIR spectroscopy may therefore be an important tool that uses compensating cations as probes to study the interactions between the cations and the structure of mica minerals.

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.

The rehydration properties and behavior of interlayer cations of Ca-, Mg-, Na-, and K-saturated homoionic saponite and vermiculite heated at various temperatures were examined and their rehydration mechanisms elucidated. The most notable features of saponite were (1) except for the Mg-saturated specimen, all saponite samples rehydrated until the crystal structure was destroyed by heating; (2) the rehydration rate in air after heating decreased in the order: K+ > Na+ > Ca2+ > Mg2+; (3) the interlayer cations apparently migrated into hexagonal holes of the SiO4 network on thermal dehydration; and (4) the b-parameter expanded on thermal dehydration. The rehydration properties and behavior of interlayer cations of vermiculite were: (1) except for the K-saturated specimen, all vermiculite samples rehydrated until the crystal structure was destroyed by heating; (2) the rehydration rate in air after heating decreased in the order: Mg2+ > Ca2+ > Na+ > K+; (3) the interlayer cations apparently did not migrate into the hexagonal holes, but remained at the center of the interlayer space, even after thermal dehydration; and (4) except for the K-saturated specimen, the 6-parameters of the samples contracted on thermal dehydration. The different rehydration properties of saponite and vermiculite were apparently due to the behavior of the interlayer cations during thermal dehydration. For rehydration to occur, the interlayer cations of saponite had to migrate out of the hexagonal holes. Consequently, saponite saturated with a large cation rehydrated rapidly, whereas saponite saturated with a small cation rehydrated slowly. On the other hand, the interlayer cations of vermiculite remained in the interlayer space; therefore, the rehydration properties of vermiculite were strongly affected by the hydration energies of the interlayer cations. Furthermore, electron diffraction patterns suggested that the saponite and vermiculite consisted of random stacking and ordered stacking of adjacent 2:1 layers, respectively. The nature of the stacking of the minerals seemed to be the most important factor controlling the behavior of interlayer cations in the thermal dehydration process.

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.

Transmission electron microscopy (TEM), including selected area electron diffraction (SAED), has been used to identify polytypes in illite, phengite and muscovite from samples representing a wide range of diagenesis and low-temperature metamorphism. Samples include Gulf Coast sediments, sediments from the Salton Sea region, California, the Martinsburg Formation at Lehigh Gap, Pennsylvania, the Kalkberg Formation at Catskill, New York, Otago Schists from southern New Zealand, pelites from the Gaspé Peninsula in Quebec, Canada, shales and slates from Wales, sediments from the Barbados accretionary complex, and synthetic hydrothermal illite.

Samples from rocks of lowest grades, including those representing a range of sedimentary diagenesis, invariably give SAED patterns with few, complex non-00l reflections which are diffuse and ill-defined and that represent largely disordered stacking sequences. Corresponding XRD patterns are consistent with 1Md polytypism. The term 1Md is therefore retained for this material. Higher grade samples, including those in which slaty cleavage is developed, and detrital grains in low-grade sediments invariably give diffraction patterns of well-ordered 2- or 3-layer polytypes. Of all samples and localities studied, only one diffraction pattern, from a sample in the Gaspé sequence, was found to be predominantly 1M. In none of the other sequences included in this study were any 1M or predominantly 1M electron diffraction patterns obtained for illite grains.

Where illite is in its original state of formation, it is consistently 1Md, whether it originates as a result of direct crystallization from solution or as a replacement of smectite. Where illite has apparently undergone subsequent change, presumably through dissolution and crystallization representing an Ostwald-step-rule-like change, it occurs as a well-ordered 2-layer (inferred to be 2M1) or, less commonly, a 3T polytype. On the basis of this limited survey, the state of polytypism appears to directly identify illite as either being in, or changed from, its initial state of formation.

Many of the presently oxidized Georgia kaolins probably existed originally in the reduced (gray) state. For that reason, the distribution of iron sulfides in presently gray kaolins may elucidate features observed in oxidized kaolins. An understanding of the nature of gray kaolins may also aid in the development of processing strategies for the exploitation of these abundant resources. The size, morphology, and degree of crystallite bonding of iron sulfides (pyrite and marcasite) in three gray kaolin cores from the Macon, Georgia kaolin district were examined by X-ray powder diffraction, X-ray fluorescence, scanning electron microscopy, and other physical and chemical methods. Pyrite and marcasite were identified as dominantly gravel- and sand-size equant crystals and crystal aggregates, rather than as framboids. Pyrite crystals commonly showed rough octahedral faces, which extended over minor cube faces. Locally, spiral growth dislocations were also observed. Marcasite was found in radiating, prismatic, and tabular crystals. In general, the marcasite crystal aggregates were much more fragile than those of pyrite. The dominance of octahedral crystal shapes and textures of the pyrite suggest inorganic precipitation from solutions supersaturated with respect to octahedral crystal faces.

Diffuse reflectance infrared (IR) spectra show that pressing kaolinite into pellets for transmission IR studies changes relative intensities of hydroxyl peaks between 3700–3600 cm-1. The magnitude of change depends on the absolute pressure, the pressing time and whether a salt matrix is used. Pressing with KBr causes larger differences than pressing neat. Diffuse reflectance IR does not require sample pressing, eliminating this variable in kaolinite studies. This improves IR's ability to distinguish kaolinites according to their hydroxyl group differences and may lead to a better understanding of kaolinite hydroxyl structures.

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.

A procedure for the determination of cation exchange capacity (CEC) and the amounts of exchangeable cations adsorbed to montmorillonite is proposed. The method consists of a single incubation of the clay in a suspension containing a low concentration of an organic dye of large binding affinity, followed by analysis of the displaced inorganic cations by inductively-coupled plasma emission spectrometry (ICPES). The CEC is obtained by taking the largest sum of displaced exchangeable cations. Montmorillonite suspensions were incubated with methylene blue (MB) or crystal violet (CV) at dye concentrations below 4 mM, for one, three or fourteen days. For total dye concentrations up to the CEC, all the dye was adsorbed and equivalent amounts of exchangeable cations were released. Both dyes could adsorb to the clay in excess of the CEC.

After one day of incubation in the presence of dye concentrations of about 50% in excess of the CEC, the total amounts of cations released were reduced to below the CEC. This reduction was interpreted as due to massive aggregation of the clay particles induced by the dye. With CV the total amounts of cations released after three or fourteen days of incubation increased and became equal to the CEC.

The same CEC was found for Na-, Ca- and SWy1 crude-montmorillonite, by employing either of the dyes.

The rehydration properties of Ca-, Mg-, Na-, and K-saturated homoionic beidellites after heating at various temperatures were compared with those of montmorillonites. The behavior of interlayer Na+ during dehydration and rehydration was also investigated by means of one-dimensional Fourier analysis. The K- and Mg-saturated specimens exhibited fast and slow rehydration rates, respectively, during exposure to air of 50% RH after heating at 800°C. These homoionic specimens showed strong rehydration properties on saturation with deionized water after heating <900°C for 1 hr. On the basis of Fourier analysis, the interlayer cations appeared to have migrated into the hexagonal holes of SiO4 network on thermal dehydration, and the migrated cations returned to the interlayer space on rehydration. This behavior of the interlayer cations appears to have been strongly dependent on value of the octahedral negative charge and on the sizes of interlayer cations. The small octahedral negative charge of beidellite produced a weaker attractive electrostatic force between the octahedral sheets and the migrated interlayer cations. Therefore, the migrated interlayer cations in beidellite were easily extracted from the hexagonal holes, and rehydration was rapid. The small cation migrated easily into hexagonal holes and was fixed to the holes. On the contrary, large cations were probably difficult to fix and were easily extracted from the hexagonal holes. Consequently, the rehydration rate of K-saturated beidellite was fast, and that of Mg-saturated beidellite was slow.

The chemical compositions of chlorite-smectite mixed-layered minerals (C/S) from the Ohyu caldera (Inoue, 1985) are analyzed using M+-4Si-3R2+ diagrams. The assumed original saponite has the following composition: Si3.54Al0.46O10Al0.173Fe2+1.385Mg1.295Mn0.02(OH)2M+0.56. Random C/S minerals (100 to 80% expandable layers) are interpreted as an interstratification of the starting 2:1 smectite layer with a A1XR2+3−x interlayer. The 2:1 smectite layer charge remains constant but Ca, Na, K cations are replaced by a Al-R2+ complex ion. The brucitic layer (produced by the polymerization of the complex ions) and the 2:1 smectite layer form a 14 Å non-expandable phase having a composition different from a true chlorite.

The true chlorite layers first appear in the ordered (corrensite) phase composed of a high charge saponite: Si3.35A10.65O10R2+3(OH)2M+0.65 and an octahedral vacancy-free chlorite Si2.90A11.10O10Al1.10R2+4.90(OH)8. The recrystallization of the original trioctahedral smectite into a high-charge saponite decreases the b-dimension difference with the chlorite component.

From these data, it is suggested that the trioctahedral smectite-to-chlorite conversion is controlled by three reactions: 1. fixation and polymerization of Al-R2+ complex ions in the interlayer region of the original smectite producing a 14 Å non-expandable phase (the interlayering of this phase with the original smectite gives the randomly interstratified C/S mineral. 2. dissolution of these random mixed-layered minerals and precipitation of corrensite. 3. dissolution of corrensite and growth of Fe-rich chlorite.

Samples from initially smectite-rich Tertiary continental volcaniclastic sediment from the Deer Lodge and Big Hole basins of southwestern Montana show a general decrease in illite/smectite (I/S) expandability with increasing burial depth. The mineralogical trends in cuttings from seven wells are interrupted by discontinuities in which I/S expandability abruptly decreases by 30 to 80%. These discontinuities coincide with stratigraphic unconformities in four wells in which the stratigraphy is known. Core samples show a wide range of I/S expandabilities over short stratigraphic intervals, possibly due to composition, porosity, and permeability variations. Sericite coexists with I/S in the deep core samples. A core sample from 7958 ft (2425 m) contains an R3-ordered I/S having a nearly ideal 3:1 illite: smectite ratio, similar to the mineral tarasovite. The structure of this I/S is dominated by stacks of four 2:1-layer fundamental illite particles and small proportions of thicker particles randomly interstratified among the four-layer particles.

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.

Hydrous phyllosilicate minerals exhibit many variations in unit-cell shape and symmetry, distortion due to cation ordering, polytypic repeats along Z, and lateral modulations that can affect the ease of indexing of X-ray powder diffraction patterns. In indexing the patterns of monoclinic and triclinic hydrous phyllosilicates it is important that the indices of all overlapping but nonequivalent lines be listed and used in the indexing program, with weights assigned according to their multiplicities. Deviations from orthogonal unit-cell geometry show up by a broadening or a splitting of nearly superimposed lines, as occurs also if the observed ß angle differs from that produced by a layer shift of ideal magnitude (e.g., a/3). Observed powder intensities should be correlated with those expected from the structure, and an index should not be assigned solely on the basis of the calculated d-value that is closest to that observed. Assigned indices should not violate space group extinctions. Multilayer structures show up in reflections of type k ≠ 3n for C-centered unit cells, not in 00/reflections.