Bromide-containing impurities were found to decrease the thermal stability of quaternary alkyl ammonium-modified layered silicates. Improved purification procedures completely removed bromide and led to a 20°C to >100°C increase in organic modified layered silicate thermal stability. Using mass spectrometry and thermal and electrochemical analysis, N,N-dimethyl-N,N-dioctadecyl quaternary ammonium-modified montmorillonite and fluorinated synthetic mica were found to degrade primarily through elimination and nucleophilic attack by these anions. The nature of residual bromides was identified and quantified, and the efficiency of removing these anions was found to be solvent dependent; sequential extraction, first ethanol then tetrahydrofuran, gave the best results. This exhaustive extraction method represents a viable alternative to the use of expensive, more thermally stable oniumion treatments for layered silicates.

X-ray powder diffraction (XRD) studies of the clay fraction of Upper Cretaceous mudstones from a shallow (2.5 km) drill hole in the Niger delta indicate a high geothermal gradient (about 100°C/km) during diagenesis. The mineralogy of the clays is similar to that observed elsewhere and consists of interstratified illite/smectite (I/S), kaolinite, and chlorite. Detrital mica and K-feldspar are also present throughout the section. The composition-depth relationship of the I/S is different from that observed in deeply buried Gulf Coast shales. The Niger delta rocks show a linear change in composition of the I/S as a function of depth in the drill hole from 60 to 10% smectite layers. The I/S ordering is R=0 in shallower samples and progresses to R=1 in deeper samples. The I/S in the deepest samples has R=3 ordering. No R=1 I/S showing a first-order 27-Å XRD reflection was found. The Niger delta sequence differs from the Gulf Coast sequence b. (1) a lack of R=1 I/S showing a 27-Å XRD reflection (which are common in Gulf Coast samples and contain 20% smectite layers), an. (2) the existence of a simple, continuous linear relation between the composition of the R=1 and R=0 I/S and depth.

A comparison of composition-temperature curves for I/S formed under different diagenetic regimes shows different types of I/S ordering in which the presence of R=1 I/S showing a 27-Å reflection and R=3 I/S types changes the composition-depth (and thus, composition-temperature) relations. These changes suggest a difference in the energy necessary to form the various ordering types. Also, geothermal gradient during burial appears to be responsible for different composition-temperature gradients found for the same type of I/S ordering.

Micromorphological studies were performed in order to understand the factors and processes involved in the formation of calcium carbonate (CaCO3) in twenty three soil series of Vertisols representing sub-humid, semi-arid and arid climatic regions of Peninsular India. The study indicates that Vertisols contain both pedogenic calcium carbonate (PC) and non-pedogenic calcium carbonate (NPC) irrespective of the ecosystems to which they belong. The NPCs are part of the parent material of Vertisols. Dissolution of NPCs and recrystallization of dissolved Ca2+ ions are responsible for the formation of PCs. Vertisols of arid and semi-arid climates contain more PC in their soil control section (SCS) than those of sub-humid climates. Formation of PC is the prime chemical reaction responsible for the increase in pH, the decrease in the Ca/Mg ratio of exchange site with depth and in the development of subsoil sodicity. Petrographic and scanning electron microscopic (SEM) examination of quartz, feldspars and micas indicate little or no alteration, discounting the possibile formation of smectite during Vertisol formation. X-ray diffraction (XRD) analysis of clays indicates that smectites of Vertisols are fairly well crystallized and do not show any sign of transformation except for hydroxy interlayering. The preservation of the crystallinity of smectite and the lack of transformation of primary minerals thus validate the hypothesis of positive entropy change during the formation of Vertisols.

The precise cause-effect relationship between CaCO3 of pedogenic and non-pedogenic origin, and exchangeable Mg, Na and Ca percentages (EMP, ESP and ECP) has been established in the study. This indicates that impoverishment of Ca2+ ions on the exchange sites of Vertisols needs to be controlled by rehabilitation methods that can replenish Ca2+ ions, and thus the study provides relevant information for future land resource management programmes not only on Vertisols of India but also on similar soils occurring elsewhere.

The combined use of electron microscopy and of selected area diffraction (SAD) has been applied to the study of montmorillonites from Wyoming and from Camp-Berteaux, of nontronite, and of hectorite. The study shows that only the elementary layers of the Wyoming montmorillonite and of the nontronite are single two-dimensional crystals. The elementary layers of the montmorillonite from Camp-Berteaux are formed by edge-to-edge associations of very small elements with mutual orientations of about 60° or multiples of 60°. The layers of hectorite are formed by edge-to-edge association of laths with fluctuations of orientation of the order of 10° rotation around adjoining edges. The SAD patterns of Wyoming montmorillonite show that the single layer plane symmetry group of this mineral is c1m1; nontronite layers belong to the symmetry group c2mm. The study of thick particles shows that in turbostratic smectites the layers are stacked with mutual rotations around the perpendicular to their plane. This mode of stacking explains the absence of hkl reflections. High resolution diffraction (HRD) patterns obtained with sample inclined to the electron beam show that only the structure of hectorite approaches the ideal model; nontronite and montmorillonite exhibit appreciable distortions with respect to the ideal model. HRD diagrams provide precise information for the refinement of the crystal structures of smectites

Yucca Mountain is being studied as a potential site in southern Nevada for an underground, high-level nuclear waste repository. A major consideration for selecting this site is the presence of abundant zeolites in Miocene ash-flow tuffs underlying the region. Beneath Yucca Mountain four diagenetic mineral zones have been recognized that become progressively less hydrous with depth.

Zone I, the shallowest zone, is 375–584 m thick in the central part of Yucca Mountain, but 170 m thick to the north. Zone I contains vitric tuffs that consist of unaltered volcanic glass and minor smectite, opal, heulandite, and Ca-rich clinoptilolite. Zone II thins south to north from 700 to 480 m and is characterized by complete replacement of volcanic glass by clinoptilolite with and without mordenite, and by lesser amounts of opal, K-feldspar, quartz, and smectite. Zone III thins south to north from 400 to 98 m thick and consists of analcime, K-feldspar, quartz, and minor calcite and smectite. Heulandite occurs locally at the top of zone III in the eastern part of Yucca Mountain. Zone IV occurs in the deepest structural levels of the volcanic pile and is characterized by albite, K-feldspar, quartz, and minor calcite and smectite.

Clinoptilolite and heulandites in zone I have uniform Ca-rich compositions (60–90 mole % Ca) and Si:Al ratios that are mainly between 4.0 and 4.6. In contrast, clinoptilolites deeper in the volcanic sequence have highly variable compositions that vary vertically and laterally. Deeper clinoptilolites in the eastern part of Yucca Mountain are calcic-potassic and tend to become more calcium-rich with depth. Clinoptilolites at equivalent stratigraphic levels on the western side of Yucca Mountain have sodic-potassic compositions and tend to become more sodium-rich with depth. Despite their differences in exchangeable cation compositions these two deeper compositional suites have similar Si:Al ratios, generally between 4.4 and 5.0. Analcimes have nearly pure end-member compositions, typical of these minerals formed by diagenetic alteration of siliceous volcanic glass; however, K-feldspars are Si-rich compared to the ideal feldspar formula.

Bulk-rock contents of Si, Na, K, Ca, and Mg of zeolitic tuffs generally differ significantly from stratigraphically equivalent vitric tuffs, suggesting that zeolite diagenesis took place in an open chemical system. Both the whole rock and the clinoptilolite are relatively rich in Ca and Mg in the eastern part of Yucca Mountain and rich in Na in the western part. The Ca- and Mg-rich compositions of the zeolitized tuffs in the eastern part of Yucca Mountain may be due to cation exchange by the sorptive minerals with ground water partially derived from underlying Paleozoic carbonate aquifers.

Diagenetic zones become thinner and occur at stratigraphically higher levels from south to north across Yucca Mountain, probably due to a higher geothermal gradient in the northern part of the area. The diagenetic zones were established when the geothermal gradient was greater than it is today, probably during the thermal event associated with the development of the Timber Mountain-Oasis Valley caldera complex north of Yucca Mountain.

Four hydrates with d(001) = 8.4, 8.6, and 10 Å (two types) were synthesized by intercalating kaolinite with dimethylsulfoxide and treating the intercalated clay with fluoride ions. X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, and kinetics of dehydration experiments have led to the identification of two types of interlayer water. One type of water (hole water) is situated in the ditrigonal holes of the silica tetrahedral surface; the second type (associated water) forms a discontinuous layer of mobile water. The 8.4-Å and 8.6-Å hydrates have only hole water, whereas the two synthetic 10-Å hydrates and halloysite(10Å) contain both hole and associated water. The hole water is probably hydrogen bonded to the basal oxygens of the silica tetrahedra or, in the 8-Å hydrates when fluorine exchanges for inner-surface hydroxyls, the water molecules may reorient and form stronger hydrogen bonds to the fluorine. Associated water forms water-water hydrogen bonds approximately equal in strength to liquid water but is less strongly bonded to the clay surfaces than hole water. At room temperature the hole and associated water in the 10-Å hydrates do not form an ice-like structure.

An experimental program was conducted to investigate the water-vapor sorption characteristics of smectite and kaolinite mixtures. End-member smectite and kaolinite were slurry-mixed together at mass-controlled ratios corresponding to 0%, 20%, 50%, 70%, 80%, 90% and 100% smectite. Vapor desorption isotherms for the mixtures were measured at 24°C for relative humidity (RH) ranging from ∼95% to 0%.

Results show that the amount of water adsorbed by the clay mixtures at a given RH increases systematically with increasing smectite content. Derivative analysis of the sorption isotherms shows evidence of transitions between the two-, one- and zero-layer hydrate-states for the smectite-rich mixtures. The transitions become less apparent as the smectite content decreases. Monolayer coverage, specific surface area, and heat of adsorption were estimated from the isotherms using BET theory. It is shown that monolayer coverage and specific surface for the clay mixtures can be reasonably approximated by weighted averaging of the end-member clay properties. General methodologies are presented for predicting the sorption behavior (i.e. soil-water characteristics) and effective specific surface area from measurements of the end-member sorption isotherms.

Silica has been intercalated in swelling clays by hydrolysis and/or oxidation of tris(acetylacetonato)siIicon(IV) cations, Si(acac)3+, and polychlorosiloxanes, (-SiOCl2-)n, in the interla-mellar regions of the minerals. The Si(acac)3+ ions have been placed on the interlamellar surfaces by ion exchange and by in situ reaction of the acetylacetone-solvated clays with SiCl4. The (-SiOCl2-)n polymers were formed in the interlayers by reaction of adsorbed benzaldehyde with SiCl4. The optimum (001) spacing observed after firing the clays in air at 500°C (12.6 Å) corresponds to the presence of a monolayer of siloxane chains. Nitrogen BET surface areas range from 40 to 240 m2/g, depending on the amount of internal surface covered by the intercalated silica. In some cases, highly ordered products were formed which exhibit four orders of (00ℓ) reflection. Interstratified products with d(001) values between 9.6 and 12.6 Å exhibit surface areas consistent with the presence of a random mixture of totally collapsed interlayers and interlayers containing siloxane monolayers. Attempts to achieve silica intercalation by hydrolysis of SiCl4 in the clay interlayers were not productive.

The isotope dilution technique using Na and Cs as index cations was used to determine the cation exchange capacity (CEC) of illite du Puy as a function of background electrolyte composition. The work showed, in accord with previous studies, that the CEC values were in the order Cs-CEC > Na-CEC. Sodium is commonly chosen as the index cation in CEC determinations using the isotope dilution method. The experimentally measured Na-CEC values for Na-illite increased from ∼75 to ∼200 meq kg−1 for NaClO4 concentrations in the range 5.6 × 10−4 to 1.25 × 10−2 M. Cesium CEC determinations showed a much less pronounced trend over a CsNO3 concentration range from 10−3 to 10−2 M. A reference Cs-CEC value of 225 meq kg−1 was chosen. Careful chemical analyses of the supernatant solutions revealed that Ca and Mg at the (sub)μmolar level were present in all the determinations, despite the extensive conditioning procedures used. Competition between (Ca + Mg) and Na for the exchange sites was put forward as an explanation for the variation of Na-CEC values. This hypothesis was confirmed in a series of single (45Ca) and double (45Ca plus 22Na) labeling experiments. Calcium-sodium selectivity coefficients (${(}_{\text{Na}}^{\text{Ca}}{\text{K}}_{\text{c}})$) were calculated from the experimental data for NaClO4 concentrations from 5.6 × 10−4 to 0.1 M and exhibited a variation from 1.6 to 14.3. A two-site cation exchange model was developed with site capacities and ${}_{\text{Na}}^{\text{Ca}}{\text{K}}_{\text{c}}$ values for each site: planar site capacity =180 meq kg−1, ${}_{\text{Na}}^{\text{Ca}}{\text{K}}_{\text{c}}^{\text{PS}}=2$; type II site capacity = 45 meq kg−1, ${}_{\text{Na}}^{\text{Ca}}{\text{K}}_{\text{c}}^{\text{II}}=80$. The model was able to predict the Na and Ca occupancies in the Na-CEC experiments over the whole range of NaClO4 concentrations. It is recommended that Cs should be used instead of Na as the index cation for determining the CEC of illite.

Iron-chromium hydroxides are important solid phases governing the aqueous concentrations of Cr(III) in soils and fly ashes. Although direct identification of noncrystalline (Fe,Cr)(OH)3 is difficult, the infrared spectra of noncrystalline Fe(OH)3 and Cr(OH)3, coprecipitated (Fe,Cr)(OH)3, and physical mixtures of Fe(OH)3 and Cr(OH)3 can be distinguished on the basis of the asymmetric stretching doublet (v3) of structural carbonate anions. As the Cr mole fraction of the coprecipitated (Fe,Cr)(OH)3 increases, the position of the low-frequency v3 peak (v3″) changes progressively to higher frequencies, and the carbonate v3 splitting decreases. No change in carbonate v3 splitting or v3″ location was observed for physical mixtures of Fe(OH)3 and Cr(OH)3. The changes in v3 splitting are believed to be caused by different degrees of polarization of the carbonate ligand by the Fe and Cr cations.

Pure Cr(OH)3 exhibits a strong affinity for carbonate and H2O and tends to remain noncrystalline even at very high pHs. In contrast, pure Fe(OH)3 gradually converts to crystalline goethite at high pH, to the exclusion of much of the H2O and carbonate. The presence of Cr in (Fe,Cr)(OH)3 solid solutions seems to inhibit the transformation to crystalline goethite. The strong association of carbonate with Cr and the kinetic inertness of Cr(III) inner-sphere complexes in general may account for the maintenance of noncrystalline solid-solution materials in lieu of transformation to a crystalline end product.

The thicknesses of fundamental illite particles that compose mixed-layer illite-smectite (I-S) crystals can be measured by X-ray diffraction (XRD) peak broadening techniques (Bertaut-Warren-Averbach [BWA] method and integral peak-width method) if the effects of swelling and XRD background noise are eliminated from XRD patterns of the clays. Swelling is eliminated by intercalating Na-saturated I-S with polyvinylpyrrolidone having a molecular weight of 10,000 (PVP-10). Background is minimized by using polished metallic silicon wafers cut perpendicular to (100) as a substrate for XRD specimens, and by using a single-crystal monochromator. XRD measurements of PVP-intercalated diagenetic, hydrothermal and low-grade metamorphic I-S indicate that there are at least 2 types of crystallite thickness distribution shapes for illite fundamental particles, lognormal and asymptotic; that measurements of mean fundamental illite particle thicknesses made by various techniques (Bertant-Warren-Averbach, integral peak width, fixed cation content, and transmission electron microscopy [TEM]) give comparable results; and that strain (small differences in layer thicknesses) generally has a Gaussian distribution in the log-normal-type illites, but is often absent in the asymptotic-type illites.

The i.r. spectra of mixtures of different Na-montmorillonites were determined at several water contents between 2 and 22 g of water/g of montmorillonite. It was found that Si—O absorption is represented by four closely-spaced bands, one of which is pleochroic. The pleochroic band appeared only at higher water contents. All of these bands, excepting that with the highest wave number, shifted in frequency with increasing isomorphous substitution. None of them shifted in frequency with increasing water content.

The absorption coefficient for the principal Si—O absorption decreased with increasing isomorphous substitution but increased with increasing water content. Niether isomorphous substitution nor water content appeared to have any significant effect on absorption due to O—H stretching or H—O—H bending in the interlayer water.

At a critical water content for each montmorillonite, an abrupt change occurred in the absorption coefficient for the principal Si—O absorption. This change was ascribed to a sudden rearrangement of the particles.

This paper describes an improved simple, sample-mounting method for random powder X-ray diffraction (XRD), namely the razor tamped surface (RTS) method, which prepares a powder mount by tamping the loose powder with the sharp edge of a razor blade. Four kaolinites and a quartz powder were used to evaluate the RTS method by quantifying the degree of orientation in the sample mounts using orientation indices. Comparisons between the RTS and other published simple methods, consisting of front loading, back loading and side loading, indicate that the RTS method produces minimum packing density and minimum preferred orientation in the powder mounts of all five samples. The quartz powder used in this study does exhibit a tendency to preferred orientation. The mechanism by which the RTS method reduces preferred orientation is examined by comparing the width of the sharp blade edge with the size of clay particles. The advantages and disadvantages of the RTS method are also discussed.

The transformation of kaolinite to halloysite-7 Å was identified in the kaolin deposit of São Vicente de Pereira (SVP), using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). Both the 02, 1̄ and 13̄, 13 reflections show changes in the XRD patterns along the kaolinite to halloysite-7 Å transition, and the FTIR spectra show changes corresponding to both OH− and Si-O-stretching bands and Al-O-Si-bending vibrations. The interlayer water content in the kaolinite structure increases during transition. The two-layer periodicity of well-ordered kaolinite and rolling up of kaolinite plates are observed using high-resolution transmission electron microscopy (HRTEM). Long and short tubes exhibit halloysite-7 Å. No structural Fe was found in the kaolinite samples. Analytical electron microscopy (AEM) indicates no substitution of Al3+ for Si4+. The Si/Al ratio shows values of ∼1 for the kaolinite and rolled kaolinite plates. The 27Al magic angle spinning neutron magnetic resonance (MAS-NMR) spectra display a resonance centered at ∼1 ppm, assigned to six-coordinated aluminum. The transformation of kaolinite to halloysite-7 Å is controlled by surface reaction.

Intercalation compounds of styrene and quaternary ammonium montmorillonite were prepared by immersion of the clay in styrene monomer. The intercalation of stearyltrimethylammonium (CH3(CH2)17N(CH3)3+)-montmorillonite and styrene showed an expansion of the basal spacing to a constant value of ∼32 Å after immersion for 10 days. After polymerization, the amount of polystyrene in the interlayer region was determined by thermal gravimetric analysis. Styrene adsorption initially increased with increasing quaternary ammonium cation and then became approximately constant when loading of the quaternary ammonium cation exceeded 100 meq/100 g clay. The volume resistivity of the stearyltrimethylammonium-montmorilionite-polystyrene complex, which was determined with a high resistance meter, was greater than that of both the quaternary ammonium-montmorillonite and the montmorillonite, and increased in proportion to the amount of polymer adsorbed. These data indicate that polystyrene improved the insulating properties of the clay films.

Burial diagenesis of shales of the Frio Formation resulted in an increase in the abundance of mixed-layer illite-smectite (I-S), albite and chlorite, and a decrease in the abundance of K-feldspar, illite and kaolinite. Some of the mineralogic trends determined in this study contrast with the results of Hower et al. (1976) and other studies of Frio shales. The differences are due to improvements in laboratory and clay quantification techniques since the time of the earlier research. I-S composition changed from ~20% to ≥80% illite, and mineralogic and chemical reaction of I-S continued throughout burial. Shale diagenesis was an open-system process that required addition of K2O and A12O3, and resulted in loss of SiO2. The amount of SiO2 made available by shale diagenesis is sufficient to be the source of the quartz-overgrowth cements in the associated Frio sandstones. The relationships between I-S diagenesis and fluid flow from shales into sandstones, generation of abnormal formation-water fluid pressure, onset of sandstone diagenesis and distribution of authigenic phases in sandstones indicate that reaction of the I-S in shales is one of the most important components of the sandstone/shale/formation water diagenetic system.

Competitive adsorption between glyphosate and phosphate on goethite was evaluated. The influence of background electrolyte on the adsorption of glyphosate and phosphate was also investigated by using 0.01 M KCl, 0.1 M KCl and 0.01 M CaCl2 as background electrolytes. Experiments showed that phosphate displaced adsorbed glyphosate from goethite, whereas glyphosate did not displace phosphate. Results also showed that the background electrolyte had a strong effect on phosphate adsorption, but little effect on glyphosate adsorption. Thus, there are differences between the adsorption of glyphosate and phosphate. The study also showed that 0.01 M KCl caused dispersion of goethite, resulting in inefficient filtering, and that phosphate precipitated as calcium phosphates in 0.01 M CaCl2 background electrolyte solutions. The results suggest that 0.1 M KCl is a more suitable background electrolyte to determine competitive adsorption processes involving glyphosate and phosphate.

The exchange reactions of Na, Ca and Mg on montmorillonite are revisited employing recently developed analytical and theoretical approaches. The fractional adsorption of the cations has been determined by displacing them from the adsorbed state in one step, using a low concentration of an organic cation of large binding affinity. The analysis of displaced and solution cations employed inductively coupled plasma emission spectrometry. An adsorption model was employed in the analysis of the data. The procedure consists of solving the electrostatic Gouy-Chapman equations and calculating adsorbed amounts of the cations as the sum of the cations residing in the double layer region, and the cations chemically bound to the surface, in a closed system. The model also accounts explicitly for cation complexation in solution. Thus the calculations also considered the adsorption of CaCl+ and MgCl+, which eliminated the apparent increase of the cation exchange capacity (CEC) with divalent cation concentration. The model could explain and yield predictions for our measured adsorbed amounts as well as previously published data, in the binary and ternary systems of Ca/Mg/Na, provided that the fraction of surface sites occupied by calcium did not exceed 0.4. For a larger coverage of surface sites by calcium, a fit of the experimental data required an order of magnitude increase in the binding coefficients of the divalent cations in the binary system Ca/Na and in the ternary system Ca/Mg/Na.

Interaction of La3+- and Ce3+-exchanged hectorites with oligomeric hydroxy-Al cations results in the formation of cross-linked hectorites possessing moderately high surface areas (~ 220–280 m2/g) and high thermal stability. The basal spacings of these products were generally in the range 17.0–18.0 A, the exact d(001) value depending on the age of the hydroxy-Al oligomeric solution and on the pH of the starting hectorite dispersion. Interaction of Li- or Ce-fluorhectorite with hydroxy-Al oligocations produced the corresponding cross-linked fluorhectorites, which showed markedly higher basal spacings (18.2–20.0 Å for air-dried samples), surface areas (~300–380 m2/g), and thermal stability, as compared with those of the cross-linked hectorites. The cross-linking agent applied in the synthesis of the hydroxy-Al hectorite and fluorhectorite products consisted of a solution of hydroxy-Al oligomers aged for periods of 7 to 27 days. A constant ratio of 2.0 mmole Al/g of smectite was used in all preparations. The high basal spacings and porosity of the newly synthesized products are consistent with a structure similar to that previously proposed for cross-linked hydroxy-Al montmorillonite.

X-ray diffraction patterns of garnierites indicate that most samples resemble serpentine-group minerals or a talc-like mineral, or a mixture of these forms, and give respectively 7 Å and 10 Å basal reflections. From a survey of some 40 garnierites, four of predominantly serpentine type and seven of predominantly talc-like type were selected for detailed study. The talc-like garnierites exhibit little variation of the 10 Å basal spacing with low-temperature heating or with immersion in liquids, though some may contain a small proportion of expandable layers. Chemical analyses show considerable deviations of octahedral/tetrahedral cation ratios from the values 3/2 and 3/4 for normal serpentine and talc minerals, and may be interpreted in terms of mixed 1:1 and 2:1 layer types, either as separate phases and/or as interstratifications, or as defect structures of various kinds. The H2O + contents of the talc-like forms of garnierite are considerably greater than that of normal talc and point to a mineral of composition 3(Mg, Ni)O·4SiO2. 2H2O or [(Mg, Ni)3Si4O10(OH)2]H2O—a talc mono-hydrate formula. The green color of garnierites is related to the NiO weight per cent and a color index is derived based on the Munsell color charts.