Clay minerals in shales from cores at Site 808, Nankai Trough, have been studied using X-ray diffraction (XRD), scanning transmission electron microscopy (STEM), and analytical electron microscopy (AEM) to compare the rates and mechanisms of illitization with those of coeval bentonites, which were described previously. Authigenic K-rich smectite having a high Fe content (∼7 wt. %) was observed to form directly as an alteration product of volcanic glass at a depth of ∼500 meters below seafloor (mbsf) with no intermediate precursor. Smectite is then largely replaced by Reichweite, R, (R = 1) illite-smectite (I-S) and minor illite and chlorite over depths from ∼550 to ∼700 mbsf. No further mineralogical changes occur to the maximum depth cored, ∼1300 m. Most smectite and I-S in shales are derived from alteration of glass, rather than being detrital, as is usually assumed. Discrete layer sequences of smectite, I-S, or illite coexist, indicating discontinuities of the transformation from smectite to (R = 1) I-S to illite. Authigenic Fe-rich chlorite forms concomitantly with I-S and illite, with the source of Fe from reactant smectite.

Smectite forms from glass with an intermediate precursor in coeval bentonites at approximately the same depth as in shales, but the smectite remains largely unchanged, with the exception of exchange of interlayer cations (K → Na → Ca) in response to formation of zeolites, to the bottom of the core. Differences in rates of illitization reflect the metastability of the clays. Temperature, structure-state, and composition of reactant smectite are ruled out as determining factors that increase reaction rates here, whereas differences in water/rock ratio (porosity/permeability), Si and K activities, and organic acid content are likely candidates.

X-ray powder diffraction (XRD), thermal gravimetric analysis (TGA), surface area measurements, and near-edge X-ray absorption fine structure (NEXAFS) spectroscopy were used to examine the surface properties of organosilane-modified smectite-type aluminosilicate clays. Organic modified clays derived from the reactions of montmorillonite (containing 93–95% montmorillonite from a bentonite, <1% quartz, and 4–6% opal CT) with octadecyltrichlorosilane (C18H37SiCl3) and octadecyltrimethoxysilane [C18H37Si(OMe)3] are highly hydrophobic. Surface loadings of the modified clays depend on the organosilane and the solvent, and they range from 10 to 25 wt. %. The organic species are probably adsorbed to the outer surfaces and bound to the edges of the clay via condensation with edge-OH groups. Encapsulation of montmorillonite with C18H37SiCl3 and C18H37Si(OMe)3 resulted in a hydrophobic coating that acts like a “cage” around the clay particles to limit diffusion. Basal spacings of the organic modified clays remain at ∼15 Å upon heating to 400°C in N2, whereas those of unmodified clays collapse to ∼10 Å. A considerable reduction in surface area (by 75–90%) for organic modified clays is observed, which is consistent with the existence of a surface coating. The solvent used can affect the amount of organic silane coated on the clay particles, whereas the difference between the products prepared using C18H37SiCl3 and C18H37Si(OMe)3 in the same solvent is relatively small. The carbon and oxygen K-edge NEXAFS spectroscopy of the modified montmorillonite surfaces showed that surface coatings on the outside of the clay particles exist. The encapsulating system may allow for economical remediation and storage of hazardous materials.

To characterize the evolution of dioctahedral interstratified clay minerals in the Golden Cross epithermal deposit, New Zealand, hydrothermally altered volcanic rocks containing the sequence smectite through illite-smectite (I-S) to muscovite were examined by optical microscopy, X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission and analytical electron microscopies (TEM/AEM).

XRD analyses of 30 oriented clay samples show a broad deposit-wide trend of increasing illite content in I-S with increasing depth and proximity to the central vein system. Six representative samples were selected for SEM/TEM study on the basis of petrographic observations and XRD estimates of I-S interstratification. Ca and Na are the dominant interlayer cations in smectite, but as the proportion of illite layers in I-S increases, so does the K content and (IVAl + VIAl)/Si ratio. Layers and packets tend to flatten and form larger arrays, reducing the amount of pore space. Smectite coexists with (R = 1) I-S, rather than being (R = 0) I-S where R is the Reichweite parameter. The highest alteration rank samples contain discrete packets of mica to ∼300 Å thick, but a limited chemical and structural gap exists between illite, which is intermediate in composition between common illite and muscovite, and illite-rich I-S. Selected-area electron diffraction (SAED) patterns of mica show that the 1M polytype dominates, rather than the common 2M1 polytype.

Petrographic, SEM, and TEM data imply that all phyllosilicates formed via neoformation directly from fluids. Relatively mature I-S and micas form simultaneously, without progressing through the series of transformations that are commonly assumed to characterize diagenetic sequences during burial metamorphism in mud-dominated basins. Although the overall distribution of clay minerals is consistent with temperature as a controlling variable, local heterogeneities in the distribution of clay minerals were controlled by water/rock ratio, which varied widely owing to different rock types and fracture control.

The clay mineral textures, assemblages, formation mechanisms, and controlling geological parameters relating to alteration of silicic volcanic rocks by hydrothermal solutions, in core samples from the Broadlands-Ohaaki hydrothermal system, New Zealand, were investigated using X-ray diffraction (XRD), scanning electron microscopy (SEM), and transmission and analytical electron microscopy (TEM/AEM). Mineralogical and textural relations of this active hydrothermal system, for which temperatures and fluid relations are well known, are equivalent to those in the Golden Cross hydrothermal gold deposit as described in Part 1.

XRD data show a sequence of clay minerals from smectite to a range of interstratified I-S to mica with increasing depth and temperature, on average. TEM observations are in general agreement with XRD data, especially with respect to relative proportions of illite (I)- and smectite (S)- like layers. TEM data also show that: (1) Smectite packets contain no discrete illite-like layers in samples identified as (Reichweite, R = 0) I-S by XRD. They coexist with separate packets of (R = 1) I-S. (2) A continuous range in I-S occurs from (R = 1) I-S with increasing proportion of illite-like layers, but at high illite-like layer contents there is a gap between I-S and illite. (3) 1M and 2M1 polytypes of mica coexist in separate packets, but the rare 1M polytype has a larger VIMg content.

The data imply that clay minerals formed by dissolution and neocrystallization directly from volcanic phases, although multiple reaction events can not be ruled out. Such “episodic” alteration produces a sequence of clay minerals identical to those of prograde diagenesis of pelitic sediments. This result implies that the presence of a continuous sequence is not definitive proof of continuous sequences of transformation as a function of time and continuous burial. Reaction progress of the clay-mineral sequence is in general accord with the known temperature gradient, but with significant and common exceptions. High porosity and permeability, both inherent in rock texture and local structure, are inferred to foster local reaction progress, as consistent with metastability of phases and the Ostwald step rule.

The Kübler Index (KI) is defined as the full width at half-maximum height (FWHM) of the 10-Å X-ray diffraction peak of illite-smectite interstratified (I-S) clay minerals. The only parameters controlling the Kübler Index are assumed to be the mean number of layers (N) in the coherent scattering domains (CSD), the variance of the distribution of the number of layers of the CSD, the mean percentage of smectite layers in I-S (%S), and the probability of layer stacking (Reichweite).

The Kübler-Index measurements on air-dried (KIAD) and ethylene-glycolated (KIEG) samples were compared to N and %S using the NEWMOD computer program to simulate X-ray diffraction patterns. Charts of KIAD versus KIEG corrected for instrumental broadening were made and isolines were mapped for constant N and %S. Isolines allow a direct and rapid determination of N and %S from KI measurements.

The method allows quantification of the metamorphic anchizone limits by considering mean thickness of fundamental particles in MacEwan crystallites. The transition from diagenesis to the anchizone and from the anchizone to the epizone of low-grade metamorphism corresponds to thicknesses of 20- and 70-layer fundamental particles, respectively.

Methylene blue (MB) was adsorbed from aqueous solutions onto a kaolinite and four soil samples to determine the effects of MB dimerization on the measured surface area. Adsorption isotherms were prepared using four adsorbing solutions containing, respectively, 9, 46, 71, and 83% of MB molecules in the dimeric state. Langmuir-type isotherms were obtained in each case. The results indicate that equilibration occurs quickly. The aggregation state of MB molecules at the surface does not depend on the aggregation state in the initial adsorbing solutions, but on the final equilibrium concentration of MB. A comparison with the specific surface area measured by adsorption of ethylene glycol monoethyl ether indicates that MB adsorbs as a monomer, regardless of the aggregation number in solution. This result occurs owing to the strength of monomer-surface and monomer-monomer interactions. If monomer-surface interactions are favored, the MB dimer adsorbs in the monomeric form. If monomer-monomer interactions are favored, dimer adsorption may occur. The visible spectra of adsorbed molecules indicated that MB was present at the surface as a mixture of monomeric and dimeric species. These results suggest that dimers are formed in the contact region between two aggregating particles.

Iron and silicon in various proportions are the major components of the newly formed hydrothermal sediments in the Atlantis II Deep, Red Sea. Iron-rich 2:1 phyllosilicates with morphologies varying from ribbons to plates represent clays in initial formation stage. Well-crystallized goethite particles contain domains of hundreds of nanometers in length with the rare presence of dislocations. Molar compositions show ratios of Si/Fe = 0.12 and Al/Fe = 0.05. Euhedral feroxyhyte with curled edges forms clusters with the goethite. The feroxyhyte has ratios of Si/Fe = 0.3 and are the major Si-associated iron oxides. Two nanometer-size phases showing short range periodity are common in the newly formed Atlantis II sediments: (1) hematite with traces of Si and (2) ferrihydrite with Si/Fe molar ratios varying between 0.17–0.89. The ferrihydrite forms large clusters. Hematite appears also as well-crystallized large crystals. Feroxyhyte probably forms at the transition zone between Red Sea Deep Water and the upper convective layer in the brine, whereas goethite and ferrihydrite form in the upper convective layer. The two forms of hematite represent two stages of recrystallization, which occur within the brine.