Hydrothermally kaolinitized muscovite from the Otago schist of Brighton, New Zealand, has been studied by transmission and analytical electron microscopy (TEM and AEM) to determine the mechanism of alteration and to compare reactant-product relations for di- and trioctahedral micas. The muscovite is a primary metamorphic phase having a phengitic composition. It occurs as well-ordered, two- and three-layer polytypes, in grains as thick as 30 μm. Kaolinite occurs as packets of layers, each about 100–600 Å thick, which alternate with packets of muscovite or smectite-like layers. Most of the kaolinite is highly disordered in stacking sequence, although a one-layer polytype is also present, occurring as relatively thick sequences of layers. Phase boundaries between kaolinite and muscovite are invariably parallel to the 001 lattice fringes with no strain contrast; i.e., no transitions exist along layers. Parallelism of 00l and 11l reflection rows of both kaolinite and muscovite implies a topotaxial intergrowth. A smectitelike phase is also present, occurring as packets of wavy layers, which locally have periodic contrast that may reflect R1 ordering of illite/smectite. This material appears to be a direct, “along-layer” alteration product of muscovite. Electron diffraction data and lattice-fringe images imply that kaolinite alternates with micaceous phase(s) with some regularity; i.e., micaceous layers are separated by approximately equal numbers of kaolinite layers. Similar long-range periodicity occurs in contrast variations within packets of kaolinite layers.

The data collectively suggest that the alteration interface was self-perpetuating and that alteration proceeded rapidly along layers once it initiated in 2:1 layers at crystal edges or strained areas, with no observable component normal to the layers. They also suggest that smectite may have formed as an intermediate phase during the hydrothermal kaolinitization of muscovite. In the previous study of alteration of biotite in the same sample, “along-layer” transition boundaries were commonly observed, and a second, intermediate product phase was not detected, implying a relation between the alteration mechanisms and the chemical differences between reactants and products.

To eliminate mercury vapor from gas streams, three major methods are used: condensation, absorption, and adsorption. This work deals with adsorption, using elemental sulfur as an active phase supported on sepiolite and palygorskite fibrous clays. Sulfur loads of 5–30% were deposited by catalytic oxidation of hydrogen sulfide at temperatures of <200°C, the clays acting first as a catalyst of the reaction and then as a carrier of the obtained sulfur. The ability of the sulfurized clay adsorbents to retain mercury was studied at 45°C and 1 mm Hg pressure. The high values found, about 4 g Hg/g S supported on clays, compared with 1.69 g Hg/g S on activated carbon under the same conditions are related to a more appropriate pore size distribution, with more of the pore widths >6 nm for the sulfurized silicates. Also, the allotropic state of the deposited sulfur, where Sπ (octo-catena) is better than Sλ (octo-cycle), may also be a contributing factor.

The safe disposal of 60Co, 63Ni, and 59Ni has required considerable information on the interactions of Co2+ and Ni2+ with clay minerals in the geosphere. X-ray photoelectron spectroscopy (XPS) has been used to probe the sorption sites for Co2+ and Ni2+ on hectorite and montmorillonite. The spectra were measured for Co-hectorite, Ni-hectorite, and Ni-montmorillonite immediately following ion exchange and after washing the clay two and five times with distilled water. The spectra, recorded following etching of the surface with an argon ion beam, differentiate two sorption sites; a labile (to washing) fraction sorbed as ion pairs, and a non-labile fraction sorbed by ion exchange at broken bond and interlamellar sites. The data were consistent with the sorption of metal ions (Co2+, Ni2+) in a common “MO6” ligand environment.

Co2+ had a greater affinity for exchange on hectorite than did Ni2+; but Ni2+ had a greater affinity for the surface of montmorillonite than for hectorite. The argon ion etching of Ni-montmorillonite gave rise to a new photopeak of 853 eV, which was probably due to elemental Ni formed consequent to the chemical violation of the surface by ion etching.

The rate of Fe(II) oxidation at a constant rate of oxygen supply in the presence of citrate was measured at pH 6.0 at various citrate/Fe(II) molar ratios at 23.5°C in 0.01 M ferrous Perchlorate system. The kinetics followed a first-order reaction with respect to Fe(II) concentration at constant pH (6.0) and aeration (5 ml/min). The rate constant decreased exponentially from 41.3 × 10-4 to 7.6 × 10-4/min with an increase in the citrate/Fe(II) molar ratio from 0 to 0.1.

The nature of the hydrolytic products formed after 120 min of oxidation was arrived at by X-ray powder diffraction (XRD), infrared spectrometry (IR), and transmission electron microscopic (TEM) analyses. In the absence of citrate, goethite (α-FeOOH) and poorly crystalline lepidocrocite (γ-FeOOH) were the oxidation products formed at pH 6.0. The formation of lepidocrocite was promoted at the expense of goethite at citrate/Fe(II) molar ratios of 0.0005 to 0.005. The formation of lepidocrocite was especially pronounced at a citrate/Fe(II) molar ratio of 0.001, as observed from the width at half height (WHH) and the area of the 020 XRD peak of lepidocrocite. At a citrate/Fe(II) molar ratio of 0.01, however, the crystallization was perturbed resulting in the formation of noncrystalline Fe oxides, and no precipitate was observed at a citrate/Fe molar ratio of 0.1. The strong complexation of Fe(II) with citrate retarded the kinetics of Fe(II) oxidation and the formation and hydrolysis of Fe(III). The complexation, electrostatic, and steric effects of the coexisting citrate anions in solution apparently influenced the oxygen coordination and the way by which the double rows of edge-sharing Fe(O,OH)6 octahedra linked during crystallization, resulting in the formation of lepidocrocite.

Direct water-activity measurements were made for calcium-smectite-CaCl2 mixtures. The samples used were prepared by high-pressure filtration and had water contents <0.60% by weight of clay. For deionized water, the water activity (aw) ranged between 1 and 0.4 and was independent of the pressure history of the clay cake. Good agreement was found with the results of an adsorption isotherm. Samples were also prepared in 1,3, and 5 M CaCl2 solutions. The final concentration of chloride present in the cakes was measured: substantial anion exclusion was observed. The water activity of the clay-salt mixtures depended on both the water content and the concentration of CaCl2. The data can be well represented by the expression aw = min(aw0, aw*c × aw*s), where aw0 is the water activity of the brine used to prepare the cake, and aw*c and aw*s are water activities calculated for clay (in absence of salt) and salt (in absence of clay), respectively. The compaction and swelling behavior of a core of the same Ca-smectite was also investigated for pressures (P) between 0.5 and 800 bar. In two compaction-swelling cycles total recovery of the void ratio (e) was observed with, however, large hysteresis in the relationship between e and P. The osmotic pressure developed in the core at equilibrium, evaluated using the water-activity data, was intermediate between the compaction and swelling pressures. Apparently, another force, Pm, linked to irreversible changes in the structure of the matrix was contributing to the resistance to compaction. Pm values agreed with literature results for Ca-smectite suspensions.

The surface free energy components of clay-organic complexes were determined to assess to what extent an organic adsorbate modified the surface properties of the mineral, insofar as the stability of soil aggregates is concerned. Adsorption isotherms for two synthetic, humic acid-like polymers were determined on a Ca-montmorillonite. From contact-angle measurements performed on dry surfaces, the surface free energy properties of the clay-organic complexes were determined using the two-liquid-phases method (water and hydrocarbons). This method allows both the dispersive and nondispersive components of the solid surface free energy, γDS and γPS, to be determined. The results show that a very small amount of polymer (1% by weight) adsorbed on the external surfaces of the montmorillonite decreased markedly the surface free energy components of the clay: γDS decreased from 75 to 28 mJ/m2 for polycondensate catechol (PC) and from 75 to 30 mJ/m2 for polycondensate catechol triglycine (PCT), whereas γPS ranged from 35 to 16 mJ/m2 (PC) and from 35 to 17 mJ/m2 (PCT). Although their chemical compositions were different, both polymers similarly modified γDS and γPS. Increasing the amount of polymer adsorbed (from 1% to 3.5% by weight) affected mostly γPS, which became as low as 5 mJ/m2; meanwhile, γDS decreased from 30 to 23 mJ/m2. Possibly, the molecular orientation of the adsorbate changed in the process of dehydration. Following adsorption of synthetic humic acid-like polymers, dry Ca-montmorillonite complexes displayed γS values < 50 mJ/m2, which were consistent with the solid-water contact angles measured in air.

Analytical, spectroscopic, and X-ray powder diffraction techniques were used to investigate the adsorption of the herbicide sodium acifluorfen (acifluorfen = 5-[2-chloro-4-(trifluorornethyl)phenoxy]-2-nitrobenzoic acid) from aqueous solution onto Cu2+-, Al3+-, Fe3+-, and Ca2+-saturated montmorillonite. As indicated by infrared and electron spin resonance spectra, which are coincident with those of the corresponding solid metal complexes, and by the basal spacings, which are the same for all the samples, acifluorfen extracted the exchangeable ions from the clay interlayer and precipitated them on external surfaces. The process involved the replacement of sodium as the saturating ion and was due to the formation of insoluble complexes between the herbicide and polyvalent metal ions.

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.

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.

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.

Core KM-3 at Searles Lake, California, comprises 693.4 m of lacustrine sediments deposited over the past 3.2 m.y. The lake water evolved from moderately saline, slightly alkaline, and dominated by Na, Ca, Cl, SO4, and HCO3 + CO3 to a highly alkaline brine dominated by Na and CO, ions. Sediments are chiefly muds and evaporites. Montmorillonite and illite are the principal detrital clay minerals supplied to Searles Lake at present and probably during the late Pliocene and Pleistocene.

The drill core is divided into three diagenetic zones on the basis of clay-mineral reactions. The upper zone (0-291.1 m) contains authigenic Fe-illite, Mg-smectite, K-feldspar, and analcime, which average 60–70% of the <2-μm silicate fraction of mud samples. The principal silicate reactants are detrital montmorillonite and kaolinite, which have been largely consumed. The middle zone (291.1–541.6 m) also contains authigenic Fe-illite, Mg-smectite, K-feldspar, and analcime, but they form only 20 to 30% of the <2-μm silicate fraction, and considerable detrital montmorillonite and kaolinite remain unaltered. In muds of the lower zone (541.6–693.4 m), a small amount of clinoptilolite is the only authigenic silicate mineral identified, although authigenic montmorillonite probably coexists here as well. Vitric ash is the silicate reactant, and detrital clay minerals apparently remain unaltered in the lower zone.

Diagenetic zoning reflects the pore-water chemistry, in which pH may have been the most important parameter. Sediments of the upper zone were deposited in highly alkaline lakes of variable salinity, and sinking brines with a pH of 9.0–10.0 have saturated all sediments. Sediments of the middle zone were deposited in lakes of moderate to high salinity. The pH was overall lower than in the upper zone, although it probably exceeded 9.0, at least locally, during silicate diagenesis. Moderate salinity and a slightly alkaline pH (~ 7.5–8.0) are inferred for both the lake and pore water of the lower zone.

Oxygen-isotope values of authigenic Fe-illite, Mg-smectite, and K-feldspar, and phillipsite in the upper diagenetic zone reflect a high degree of evaporative concentration and presumably of salinity. Equilibrium water values calculated for 22°C from the oxygen-isotopic composition of authigenic phyllosilicates range from −3.5 to +1.9%, averaging −1.2% (SMOW). Higher salinities are suggested for K-feldspar, for which water values range from +1.8 to +4.8%, averaging +3.4‰ The water value for phillipsite is +0.3‰ By comparison, rainfall at Searles Lake has an average δ18O value of about −9.8%, and a brine sample has a value of +4.0‰

Mud samples of the middle and upper diagenetic zones tend to be rich in Fe-illite or Mg-smectite, but not in both, indicating that the two minerals are favored to some extent by different environments. Fe-illite seems to be generally favored by oxidizing conditions and probably by a playa environment, and Mg-smectite seems to be favored by reducing conditions and an open-water environment. One strati-graphic unit of the upper zone does not fit this pattern and contains abundant Fe-illite in sediments of a deep perennial lake.