X-ray diffraction of four natural samples of ferrihydrite indicates the presence of crystalline domains within the primary particles. The average diameter of the primary particles (determined from low-angle powder patterns) decreases from 4.1 nm to 2.5 nm as the domain size in the xy-plane (determined by applying the Scherrer equation to the broad [110] XRD peak at 0.26–0.27 nm) decreases from 1.0 nm to 0.77 nm. The Si content (measured by acid-oxalate extraction) increases from 4.1% to 6.1% as both the domain and particle sizes decrease; other factors, however, are likely to be important in influencing particle size. For one sample of ferrihydrite, the smallest possible domain (i.e., c = 0.94 nm in the z-direction) contains 36 O atoms and three Si atoms. A model for ferrihydrite is suggested in which silicate bonds to, and bridges, the surfaces of the domains. The model can account for several aspects of the behavior of siliceous ferrihydrites.

Authigenic chlorites and illites coexisting in clastic reservoir sandstones have been studied by energy dispersive X-ray spectroscopy (EDS) in the transmission electron microscope (TEM). All 16 samples studied are drill or sidewall cores from sandstones of relatively uniform age situated offshore Norway with burial depths ranging between 2400 m and 5000 m and representing temperatures between 90°C and 180°C. Chlorites and illites with authigenic equilibrium type texture and morphology were analyzed by EDS. Tetrahedral Al and octahedral Fe+Mg in chlorite increases with burial at the expense of Si and vacant octahedral positions in the chlorite structure. Illites show a clear increase in K. These factors indicate that a continuous chemical modification of these minerals takes place in the diagenetic interval studied through continuous dissolution and precipitation reactions.

Five montmorillonites, one hectorite, and two vermiculites were treated with OH-Al solutions containing rapid- and slow-reacting polymers of similar concentrations. With all smectites, both rapid- and slow-reacting OH-Al polymers were much more preferentially adsorbed than monomeric species. Relatively slow-reacting OH-Al polymers were more preferentially adsorbed than rapid-reacting ones. The average basicity of the adsorbed Al was 2.46, which was close to that of the OH-Al polymers in the original solution. The OH-Al polymers that enter the interlayer resemble those in original solutions.

With vermiculites, the solution concentration of rapid-reacting OH-Al polymers was much reduced after reaction. The average basicity of the adsorbed Al was 1.99, which was considerably lower than that in the original solution. It is postulated that OH-Al polymers break to monomeric Al ions and then enter the clay. The monomeric Al species that enter the clay interlayers hydrolyze and polymerize in situ and become fixed. The H+ ions released from hydrolysis convert the rapid-reacting OH-Al polymers to monomeric Al in solution. Limited amounts of slow-reacting polymers were adsorbed because of their resistance to acid depolymerization.

The internal equilibrium status among chlorite-illite pairs has been evaluated through coupled substitution reactions. Compositional data of chlorites and illites from arenites at present burial temperatures between 90° and 180°C have been used to calculate end member activities and reaction quotients of the combined Tschermak reaction:

$Muscovite+Clinochlore=MgAl-celadonite+Amesite.$

The reaction quotient data in the 90° to 180°C temperature range have then been compared with the equilibrium curve for the same reaction, and found to be in reasonable agreement. This indicates that chlorites and illites in these arenites grow at near equilibrium conditions.

The data set has also been compared with chlorite-illite pairs from hydrothermally altered arenites of the Salton Sea area. For chlorite-illite containing assemblages, these data agree well with the diagenetic ones. The introduction of biotite at higher temperatures alters with the iron-magnesium distribution and breaks down the substitution relationship between chlorite and illite.

The model predicts an increasing stability of muscovite and clinochlore components with increasing temperature, while celadonite and amesite would be stabilized with increasing pressure. This is consistent with high pressure occurrences of phengite. However, at the low pressure region of diagenesis and hydrothermal alteration, the temperature effect is dominant.

High-resolution solid-state, fluorine-19, magic-angle spinning-nuclear magnetic resonance spectroscopy (MAS-NMR) was used to study natural and synthetic fluorinated 2:1 layer silicates of known composition. This technique enabled us to determine directly the coordination of structural fluorine and it was found to be sensitive to both the chemical nature of the octahedral elements (Al, Mg, Li) and the type of octahedral sheet (di- or trioctahedral). The observed chemical shifts at −132, −152, −176 and −182 ppm (relative to CFC13) were assigned to different environments of fluorine. The results were then used to characterize synthetic 2:1 layer silicates with unknown octahedral composition.

Shales have often been cited as the source of authigenic material that occurs in coarser grained sediments, but there are few comprehensive studies of diagenesis in shales that rigorously attempt to determine if they are sources for potentially mobile constituents or if they retain those constituents within the shale body. The silicate diagenesis of a Lower Cretaceous marine mudstone, the Harmon Member, was investigated by determining the bulk chemistry, clay mineral compositions and mineral modes using standard analytical techniques and linear programming. Changes in mineralogy are observed in hemipelagic laminated mudstones (LM) that are attributable to diagenesis despite relatively constant bulk compositions. These include authigenic kaolinite formation and illitization of detrital muscovite, K-feld-spar and authigenic kaolinite. No diagenetic trends in mineralogy are observed in rapid and episodically deposited transition zone (TZ) sediments because of primary (depositional) mineralogical variability. Diagenetic changes in mineral modes for shales of the Harmon Member are small, suggesting that silicate diagenesis proceeds under relatively “closed system” conditions. The occurrence of authigenic quartz suggests that much of the Si released from the dissolution of quartz and chert is precipitated within the Harmon Member. Al, Ti, and K apparently are conserved. Burial induced increase in temperature is inferred to be the primary control on silicate diagenesis within the Harmon Member.

In the copper deposit of Salobo 3A (Brazil), nontronite-like clay samples were found at the bottom of the weathering blanket. Samples were fractionated first by sedimentation and then by a HGMS method. From XRD data, it was found that the samples are essentially smectite with kaolinite in very small quantities. The average structural formula of the smectite, presented in the traditional manner, is:

Chemical analyses show that the smectite samples contain a population of clay particles whose chemistry ranges between a nontronite end-member and an Al-Mg beidellite end-member.

Spectroscopic studies by FTIR, Mössbauer, and ESR show that the three major octahedral cations (Al, Fe, Mg) are present in each octahedral sheet of the smectite, forming a solid solution, and that the chemical trends of the smectite clay detected at a “macroscopic” scale (associated clay particles) can also be observed at the unit cell scale.

Sediments from depths to 670 m in the Barbados accretionary complex and transecting the décollement zone have been studied by transmission and analytical electron microscopy (TEM/AEM). The sediments consist of claystone and mudstone intercalated with layers of volcanic ash. Smectite comprises the bulk of the noncalcareous sediments and forms a continuous matrix enveloping sparse, irregular, large grains of illite, chlorite, kaolinite and mixed-layer illite/chlorite of detrital origin at all depths. The detrital origin of illite is implied by illite-smectite textural relations, well-ordered 2M polytypism, and a muscovite-like composition. K is the dominant interlayer cation in smectite at all depths, in contrast to the Na and Ca that are normally present in similar rocks.

Deeper samples associated with the décollement zone contain small (up to 100 Å thick) illite packets included within still-dominant subparallel layers of contiguous smectite. AEM analyses of these packets imply illite-like compositions. Selected area electron diffraction (SAED) patterns show that this illite is the 1Md polytype. Packets display step-like terminations like those seen in illite of hydrothermal origin. The data collectively demonstrate that smectite transforms progressively to illite via a dissolution-recrystallization process within a depleting matrix of smectite, and not by a mechanism of layer replacement. This illite seems to form at depths as shallow as 500 m and temperatures of 20°-30°C, which is in marked contrast to the much higher temperature conditions normally assumed for this transformation. This implies that the high water/rock ratios associated with the décollement zone are significant in promoting reaction.

One Tertiary and two Cretaceous gray kaolin sites in Georgia were examined using X-ray radiography of core sections to determine the processes of formation of the deposits. The Tertiary kaolin was oxidized in the upper 3 m of the deposit and reduced below that point. The two Cretaceous kaolins were reduced from the top of the deposit to an abrupt boundary with oxidized red kaolin below. Radiography of the first Cretaceous core revealed thin laminar bedding in the gray kaolin and in the underlying red kaolin. The laminae continue without interruption across the gray kaolin/red kaolin boundary. The laminae were not visible in the gray kaolin except in radiographs. Sedimentary bedding was not observed visually or radiographically at the Tertiary site nor in sections of the core from the second Cretaceous site where kaolinite was recrystallized to large vermiforms. The original sedimentary structure in the first Cretaceous kaolin was preserved possibly due to the inhibition of kaolinite recrystallization by a higher organic matter content. Recrystallization of kaolinite and iron compounds may have destroyed sedimentary structures in part or all of the other two kaolin cores. It is hypothesized that the first Cretaceous physical and biological mixing. The same hypothesis may apply to the other two kaolins but recrystallization after deposition has destroyed sedimentary structures.

Noncrystalline aluminosilicates termed allophane and imogolite are common constituents of spodosols, soils derived from volcanic ash, and many inceptisols. The surface charge characteristics of their synthetic analogues may be used to better understand their ion retention properties. In this study, we determined the point of zero salt effect (PZSE) by potentiometric titration of allophanes with Al/Si ratios of 1.12, 1.52, and 2.04 and of imogolite with an Al/Si ratio of 2.02. We also used microelectrophoresis to determine the point of zero charge (PZC) at the particle shear plane for the same materials in CI solutions of Li, Na, Cs, and tetramethyl ammonium. The PZSE decreased with decreasing Al/Si ratio for the allophanes, but the imogolite PZSE was much lower than that of the allophane with 2.04 Al/Si. The PZC was always higher than the PZSE of the same material, especially for imogolite. The results are best explained if cations reside within the hollow tubes of imogolite. This conclusion is supported by a fluorescence study that showed that only quenchers smaller than the inner diameter of the imogolite tube could fully quench Ce-imogolite.

This paper aims at characterizing the morphology, texture, and microstructure of three hydrated kaolin rich clays (f < 0.2 μm) from volcanic soils. These clays represent a weathering sequence in which CEC, halloysite content with respect to kaolinite, as well as smectite content in the halloysite-smectite mixed-layer clays decrease with increased weathering. The clay samples were made homoionic (K+ or Mg2+) and hydrated under a low suction pressure (3.2 kPa). After replacing water by a resin, ultrathin sections were cut and examined by TEM. Particle shape varies with increased weathering, as follows: spheroids → tubes → platelets. Higher aggregation and dispersion are observed by TEM after Mg2+ and K+ saturation, respectively, at two levels of the clay-water system organization: intraparticle and interparticle. The microstructure variations induced by the nature of the exchangeable cation become less pronounced with decreasing layer charge of the 2:1 layers. They are thus related here to the presence of smectite layers localized in the halloysite habitus, mostly at the particle periphery. These results show that small amounts of smectite largely affect the organization of clays rich in kaolins at a high water content, and that K+ behaves here as a dispersing ion.

Inverse gas chromatography at infinite dilution, employing alkanes and alkenes as probes, has been used to characterize the surface properties of a series of smectites of varying chemical composition. The results of this study show that the acidic centers and the interlayer distances have a great influence on the specific interaction of the smectite surface with π-bonds of alkenes. High values of the specific interaction parameter, ɛπ, are caused by the existence of strong acidic centers that are connected with interlayer cations as well as with the chemical structure of the mineral sheets. On the other hand, alkanes, whose interaction with the smectites is predominantly dispersive, are unaffected by changes in the clays’ composition and/or structure.

Boron adsorption at constant ionic strength [0.09 ± 0.01 moles/liter of KClO4 or Ca(ClO4)2] on 0.2−2 μm clay fraction of pretreated kaolinite was modeled using both phenomenological equations and surface complexation reactions. Phenomenological equations were expressed as linear relationships between the distribution coefficient and adsorption density or equilibrium concentration. The normalized form of the isotherms allowed the distribution coefficient to be predicted over a wide range of adsorption densities or equilibrium concentrations and pH. The Langmuir isotherm revealed a weak two-part linear trend supported by a similar behavior of the van Bemmelen-Freundlich isotherm. Potential adsorption mechanisms were assessed from these isotherms. The bases for the inner-sphere (surface coordination) and outer-sphere (ion-pair) surface reactions were postulated, and equations were developed and incorporated into the generalized triple-layer surface-complexation model [TL(g)-SCM]. Boron adsorption was best modeled using the inner-sphere complexes. The results confirm that the generalized triple-layer surface-complexation model can provide information regarding plausible reactions at the substrate/aqueous interface. Intrinsic constants for postulated surface reactions were derived as fitting parameters over a range of pH and initial boron concentrations.

Investigation of mixed-layer illite/smectites with far-infrared (FIR) spectroscopy indicates the presence of torsional mode absorption bands associated with interlayer fixed-K sites. By contrast, hydrated montmorillonitic interlayer cation sites are transparent in the far IR. The presence or absence of bands for interlayer cation sites appears to be related to both the magnitude and site of negative layer charge within the 2:1 layer structure. The bimodal nature of illite/smectite spectra leads to the suggestion that two different fixed-K environments occur within illite/smectite structures. These two environments are controlled by the composition of the octahedral sheet. The torsional modes at 112 and 89 cm-1 represent fixed-K sites influenced, respectively, by an Al-rich, high-charge dioctahedral layer and a heterogeneous Al-Fe-Mg-bearing, low-charge layer. A general trend of increasing absorption of the 112 cm-1 band, relative to the 89 cm-1 band, is observed in a typical diagenetic illite/smectite sequence of Miocene shales from the Gulf of Mexico sedimentary basin. The absorbance strength of both torsional bands is also seen to increase with increasing degree of illitization and the amount of fixed potassium in the illite/smectite. These observations are consistent with the concept of shales undergoing illitization during burial diagenesis by both the collapse of high-charge smectite layers to form illite layers (i.e., transformation) and the formation of new high-charge (-0.9) illite layers at the expense of smectite layers (i.e., dissolution/ neoformation).

The reactions between montmorillonite and carbonates and hydroxides of Na, K and Li were studied at 550°C as a function of salt content and time. The reactions were found to be rapid with a half-time of 20–30 minutes. Good agreement was obtained between theoretical and experimental stoichiometric values for the clay-carbonate reaction. The 001 and 02,11 reflections of the products of the clay-salt reactions diminished in intensity and/or disappeared at and above the stoichiometric concentrations of the reactants.

Silcretes developed within the in situ regolith in the Barr Smith Range, Western Australia, were investigated using optical and electron-beam techniques. One of the cementing agents in these silcretes showed gel-like optical properties and had a variable aluminosilicate chemical composition at the scale of electron microprobe analysis so that it might be considered as allophane-like material. High resolution transmission electron microscopy demonstrated that the material consists of a fine-grained and poorly ordered kaolinite embedded in a matrix of amorphous silica.

Hydroxyaluminosilicate (HAS) ions prepared from hydroxy-Al (HyA) ions and orthosilicic acid at different NaOH/Al molar and Si/Al atomic ratios were fixed in the interlayer spaces of vermiculite (Vt). The electric charge and surface characteristics of HAS-Vt and HyA-Vt complexes formed were investigated in the pH range of 4 to 8. At pH 4 to 6, the magnitude of negative charge (CEC) of HAS-Vt and HyA-Vt complexes was drastically reduced by a HAS- or HyA-interlayer formation of Vt. At pH 7 to 8, especially in NaOH/Al molar ratio of 2.5, the magnitude of negative charge was from 62 to 89% of CEC in untreated Vt, suggesting that part of HAS or HyA ions fixed on Vt was excluded from its interlayer spaces. The positive charge did not develop on HAS-Vt and HyA-Vt complexes at pH between 4 and 8. The fixation of HAS or HyA ions on Vt caused the significant reduction of its total and internal surface areas as well as the slight increase of its external surface area. The HAS- or HyA-fixation in the interlayer spaces of Vt was confirmed by X-ray diffraction analysis. Our results provided evidence of a possibility that Vt could fix HAS ions in the same way as HyA ions, transforming to chloritized-Vt. These interlayer materials could play a significant role in modifying the surface and mineralogical properties and cation exchange capacity of clays and soils.

NMR spectra of PF1-1 Floridan palygorskite strongly suggest that Al3+ occurs only in octahedral coordination. X-ray microanalysis of the palygorskite fibers indicate a chemical composition defined by the atomic ratios: Mg/Si = 0.34, Al/Si = 0.27, and Fe/Si = 0.04. Considering the NMR and CEC data in this report along with the previously published results of IR and Mössbauer spectroscopic studies, the following structural formula is proposed for PF1-1 palygorskite:

$${\rm{(M{g_{2.12}}A{l_{1.68}}F{e^{3 + }}_{0.24}{\square _{0.96}})S{i_8}{O_{20}}{(OH)_2}{(O{H_2})_4}}}$$

The dehydration and migration of the interlayer cation of the synthetic beidellite Na0.7Al4.7Si7.3O20-(OH)4·nH2O, were studied with solid-state 23Na and 27Al MAS-NMR, heating stage XRD, and thermogravimetric analyses (TGA, DTA). The 23Na MAS-NMR of Na-beidellite at 25°C displays a chemical shift of 0.2 ppm, which indicates a configuration comparable with that of Na+ in solution. Total dehydration proceeds reversibly in two temperature ranges. Four water molecules per Na+ are gradually removed from 25° to 85°C. As a result, the basal spacing decreases from 12.54 Å to 9.98 Å and the Na+ surrounded by the two remaining water molecules is relocated in the hexagonal cavities of the tetrahedral sheet. The chemical shift of 1.5 ppm exhibited after the first dehydration stage illustrates the increased influence of the tetrahedral sheet. The high local symmetry is maintained throughout the entire first dehydration stage. During the second dehydration, which proceeds in a narrow temperature range around 400°C, the remaining two water molecules are removed reversibly without any change of the basal spacing.

FTIR studies of six partially-deuterated montmorillonites (MS) reveal the presence of two O-D stretching bands, one between 2702–2728 cm-1 and another near 2680 cm-1. For homoionic (Li, Na, Mg, Ca, or La) Wyoming-type MS, the position of the higher frequency band, designated as (O-D)h, is between 2714–2728 cm-1, whereas for homoionic Cheto-type MS it is between 2702–2706 cm-1. The lower frequency band, designated as (O-D)1, is in the narrow range of 2674–2684 cm-1. Resolution of two corresponding O-H bands, appearing near 3670 and 3635 cm-1, was observed only after partial dehydroxylation of the smectites. The changes in the relative intensities of the two O-D stretching bands as a function of the smectite type and of the Lewis acidity (charge density) of the exchangeable ion were determined. For Wyoming-type MS, the intensity of the (O-D)h band is much lower than that of the (O-D)l band, whereas for Cheto-type MS, the intensity of the (O-D)h band is about equal or slightly higher than that of the (O-D)l band. The observed resolution can be ascribed tentatively to the presence of (at least) two types of octahedral OH groups in the smectites, the (O-D)h band being assigned to AlMgOH and the (O-D)1 band to AlAlOH groups. Pillaring of Cheto-type MS with hydroxy-Al13 oligocations resulted in products showing much higher thermal stability between 400–600°C compared to that of identically pillared Wyoming-type MS. Compositional and other factors, e.g., CEC values and mode of pillaring, may cause this difference in stability.