Precise information on the location of charge in clay minerals and their charge density in smectite-dominant soils is rare. The present study was undertaken with three benchmark Vertisols to establish the relationship between the clay cation exchange capacity (CEC), charge density, as well as the location of charge in smectitic soil clay minerals and their relationship with potassium (K) fixation and release. Potassium fractions and their threshold levels in the Vertisols were determined by standard methods. Soils were segregated into silt, total clay and fine clay fractions for X-ray diffraction analysis and fine clay fractions were used to determine the CEC using standard methods. The Hofmann-Klemen effect (HK) and modified Greene-Kelly test was done with the fine clay to determine the CEC of the tetrahedral sheet. Subsequently, the CEC of the octahedral sheet was calculated as the difference between total CEC and the tetrahedral CEC. The results showed that ~60–64% of the total CEC is attributed to the tetrahedral layers. The tetrahedral CEC that is proportional to the tetrahedral charge density was significant and negatively correlated with K release threshold values and all fractions of K. The tetrahedral CEC contributed more toward the K fixation and release than the octahedral CEC. The study shows that the dominant presence of high-charge smectites in the fine clay fractions of these Vertisols contributed to the tetrahedral CEC and consequently to the charge density of these soils, which implied a tendency to fix K easily and release it with greater difficulty compared to soils with low-charge smectites.

The fine silt (2–5 μm) coarse clay (0.1–2 μm) and fine clay (<0.1 μm) fractions of a Vertisol from South Italy were studied with X-ray diffraction. The most reactive fine clay (<0.1 μm) fraction was investigated in detail using a curve decomposition method analysis of X-ray diffraction diagrams, FTIR spectroscopy and chemical analysis. In the soil parent material, the fine clay fraction was dominated by low-charge smectites (beidellite and montmorillonite) whereas, high-charge beidellite was the dominant clay mineral in the fine clay from the upper soil horizons. This suggested that high-charge beidellite was produced through alteration of the preexisting low-charge smectites and was the stable clay phase in this soil environment, characterized by high pH (>8.0). After K-saturation and 25 wetting and drying cycles, the high-charge beidellite from the soil horizons lost expandability far more than the original low-charge smectites.

The use of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in colloid science has continued to the present day in spite of the inability of this theory to explain, even qualitatively, numerous phenomena exhibited by clays and other colloidal materials. An alternative description of the fundamental forces involved in the formation of dispersions and gels was presented in 1938 by Langmuir, but was never widely accepted among colloid scientists. Recent experimental and theoretical work, particularly in Japan, has revived this alternative view, in which a long-range Coulombic attraction force appears to explain several phenomena, particularly transitions among ordered and disordered phases of colloidal particles in dilute salt solutions.

Examples are given from surface chemistry where rather complex models based on diffuse double layer theory are used to explain chemical adsorption behavior that often has a simpler explanation. It is argued that the rule of parsimony (Ockham's Razor) should be applied to complex models that appear to explain the data at hand before such models are taken to be generally valid. A satisfactory fit of model predictions to experimental data obtained under a very limited range of conditions does not prove the validity of the model. Thus, it is concluded that the DLVO theory and its modifications fail to meet the 2 criteria necessary to the acceptance of a theory: agreement with observations and simplicity.

A series of organo-montmorillonites and organo-hectorites was prepared by complete ion-exchange from the pure sodium form of the parent smectites. The organic cations were tetramethylammonium, trimethylated quaternary ammonium derivatives of the lysine and of the ornithine methyl esters, quaternarized polyammonium cations, or tetraphenylphosphonium (TPP). These organo-smectites were used as packing material for gas chromatography columns. Mixtures of light hydrocarbons (methane to n-butane; “C1” to “C4”) could be separated. The degree of separation depends on the presence of micropores or of organophilic mesopores. The BET surface area, the micropore and mesopore volumes, as well as the size distribution of micropores and mesopores were measured for several systems. As a general trend, the retention times of the light hydrocarbons decrease with an increase of the micropore volume. In the case of TPP-montmorillonite, characterized by a large mesopore volume but for which no microporosity could be detected, separation of longer linear hydrocarbons (n-pentane to n-octane) could also be achieved.

The adsorption of the sulfonylurea herbicide rimsulfuron, [N-((4,6-dimethoxypyrimidin-2-yl)aminocarbonyl)-3-(ethylsulfonyl)-2-pyridinesulfonamide], on clay minerals with different saturating cations was studied. Three smectites with different lattice charge distribution (hectorite, montmorillonite and nontronite) were selected and made homoionic to Ca2+, Cu2+ and Al3+. Because of the instability of rimsulfuron in water, the experiments were carried out in chloroform solution. The interaction mechanism depends on the nature of the saturating cation and the tetrahedral layer charge of the silicate. Among the exchangeable ions studied, only Al3+ is able to produce degradation of the herbicide to N-(4,6-dimethoxypyrimidin-2-yl)-N-[(3-(ethylsulfonyl)-2-pyridinyl]urea. In this case, the lower the tetrahedral charge, the more active the degradation. The Ca2+-saturated clays are ineffective in the degradation. In contrast, the formation of a stable chelate complex with the saturating ion permits rimsulfuron to be adsorbed to a rather high extent into Cu(II)-clays and to be stable against degradation.

Shortly after construction of a subdivision in the southwest Denver metropolitan area in 1986, a portion of the subdivision built directly on steeply-dipping strata of the Pierre Shale began experiencing damaging differential movements, causing house foundations to fail and pavements to warp and crack. This formation is a Late Cretaceous marine clay-shale composed predominantly of fluvial mixed-layer illite/smectite and quartz. During deposition of the shale, periodic and explosive volcanism generated thin beds of bentonite, consisting initially of volcanic ash and subsequently altered to nearly pure smectite. Some of these bentonite beds were exposed in a trench adjacent to the subdivision and perpendicular to the strike of the steeply-dipping strata. The thickest bentonite beds correlated well with linear heave features that these beds parallel the bedrock strike throughout the subdivision were mapped via severely deformed pavements. Mineralogical data show the bentonite bed that correlates with the worst damage within the subdivision consists of about 62% smectite by weight with mixed-layer illite/smectite expandability of 92%. By comparison, a sample of the typical silty claystone, which is fluvial mixed-layer illite/smectite mixed with detrital quartz from the adjacent strata, had about 23% smectite by weight with 70% to 90% illite/smectite expandability. Geotechnical tests for swell potential show that samples of 2 bentonite beds swelled 39% to 43% compared to 2% to 8% for samples of the typical silty claystone. It is proposed that differential swell resulting from stratigraphically-controlled differences in clay mineralogy and grain-size is the primary factor controlling extreme damage for this geologic setting.

In Northwestern Mexico, the Miocene basins that disrupted the Sierra Madre Occidental Province are filled with sandstones and conglomerates (the Báucarit Formation) cemented mainly by zeolites of the heulandite-clinoptilolite group. Few volcanic tuffs are intercalated in the sediments for which four different groups of samples have been defined. These groups correspond to a gradation in the alteration of the glassy matrix. Group 1 is characterized by the preservation of the glassy matrix and the presence of disseminated patches of clay minerals with a continuous variation between aluminous Al-montmoril-lonite and ferric smectite end-members. Heulandite-group zeolites and opal C-T are also present. Group 2 is characterized by a nearly complete replacement of volcanic glass by a more homogeneous Al-montmorillonite. In some samples, heulandite-group zeolites are present as clusters on clay minerals. The primary vitroclastic texture is generally preserved and relict glass is present in small amounts. In group 3, the secondary assemblage is dominated by heulandite-group zeolite crystals as pseudomorphs of shards and pumiceous fragments. Discrete illite is present in all samples. Textures are exceptionally well-preserved. Group 4 is characterized by the presence of heulandite and clay minerals in which the Mg-Fe smectite end-member is more magnesian than in other groups. The original texture is not preserved.

The following are deduced from the mass-balance calculations: the alteration of the tuffs leads to a strong Mg- and Ca- and, to a lesser degree, Fe-enrichment, and to Na and K depletion. Zeolites account for Ca-enrichment and clay minerals are host for Fe and Mg. As a consequence, alteration may have occurred under open system conditions and the most likely source for the high Ca and Mg gains is a fluid circulating through the underlying volcaniclastic sediments and underlying mid-Tertiary volcanics of the bimodal (basaltic-rhyolitic) sequence. However, those fluids may have been rather dilute and weakly alkaline.

As estimated temperatures are between 85 and 125°C and as there is only a low burial, it is proposed that hot fluids are responsible for the alteration of volcanic glass. A decrease with time in the initial permeability of the tuffs is consistent with the observed evolution of the changing Al-smectite toward a more magnesian composition.

Hydrothermal treatment of a mixture of silicic acid, cobalt chloride, sodium dithionite and sodium hydroxide at 250 °C under 500 psi of argon produced a pink solid. X-ray powder diffraction (XRD), transmission electron microscopy (TEM) and electron diffraction data showed the product to be a well-crystallized smectite. SEM/EDX analysis gave a unit cell formula of [(Si8.05)(Co5.58)O20(OH)4]Na066. Heating the same mixture at 150 °C without argon gave a less well ordered smectite of composition [(Si7.93)(CO5.92)O20(OH)4]Na0.42. Two peaks were observed in the cyclic voltammograms of electrodes modified with films of these two clays recorded for the blank electrolytes in the absence of any adsorbed electroactive species. The first peak was attributed to the oxidation of a small fraction of the Co2+ sites within the clay lattices to Co3+. The second peak was assigned to further oxidation of these Co3+ to Co4+.

Microbial reduction of clay mineral structural Fe(III) decreases the swelling of nontronite gels, most importantly at intermediate oxidation states (40 to 80 cmol Fe(II) kg−1 clay). The purpose of this study was to establish whether microbial reduction of structural Fe(III) decreased the swelling of other Fe-bearing smectites and to discern the influence that organic compounds of microbial origin (bacterial cells, cell fragments and/or exudates) may have on clay swelling and texture. Structural Fe(III) was reduced by incubating smectite suspensions with either a combination of Pseudomonas bacteria or a mixture of anaerobic bacteria. The influence of organics on clay swelling was estimated on smectites suspended in either organic or inorganic media in the absence of bacteria. The gravimetric water content of the reduced clay gels equilibrated at various applied pressures was recorded as a function of Fe oxidation state. Transmission electron microscopy (TEM) was employed to determine the influence of bacteria and type of media on the texture of reduced smectite gels. Reduction of structural Fe(III) by bacteria decreased the swelling pressure of all Fe-bearing smectites. Increased clay swelling, due to the presence of organics (organic medium, exudates or cell fragments), was correlated to the total Fe content, the extent of structural Fe reduction, as well as the initial swelling characteristics of the Fe-bearing smectites. High structural Fe(II) contents (>50 cmol Fe(II) kg−1) resulted in increased attractive forces between clay platelets that decreased clay swelling, even in organic medium suspensions. Microbial reduction resulted in increased face-face association of individual clay layers, forming larger and more distinct crystallite subunits than in nonreduced clay gels. But, perhaps more importantly, microbial reduction of structural Fe(III) resulted in an increased association between crystallite subunits and, thus, an overall larger particle size and pore size distribution, due to the interaction of bacteria ceils, cell fragments and organic exudates.

Transmission electron microscopy (TEM) including high-resolution transmission electron microscopy (HRTEM) and analytical electron microscopy (AEM) were used to study the fine clay fraction (<0.1 μm) from the eluvial E horizon of podzols located in central Finland that had developed from till materials. Soils of increasing age (6500-9850 y BP) were selected to represent a chronosequence of soil development. Expandable phyllosilicates (vermiculite, smectites) are formed in the eluvial E horizon of podzols in a short time (6500 y). TEM observations show that dissolution and physical-breakdown processes affect the clay particles. As the age of the soils increases, fragmentation and exfoliation of large precursor minerals lead to thinner clay particles of two to three layers thick. The chemical compositions of individual particles obtained by AEM indicate that expandable phyllosilicates from the E horizon of podzols are heterogeneous, involving a mixture of vermiculite, Mg-bearing smectites, and aluminous beidellite. Results suggest that heterogeneity is related to the nature of their precursors. Vermiculite and Mg-bearing smectites are derived from biotite and chlorite weathering whereas phengitic micas alter to aluminous beidellite. Because the transformation of biotite and chlorite is more rapid than phengitic micas, biotite and chlorite contributes predominantly to smectites in the younger soils, as long as ferromagnesian phyllosilicates are present in the E horizons. If not, a larger proportion of smectites is derived from phengitic micas in the older soils. Direct measurement of d(001 ) values on lattice fringe images from alkylammonium-saturated samples shows that interlayer charge varies from high-charge expandable minerals (0.6–0.75 per half unit cell) in the younger soils to 0.5–0.6 per half unit cell in the oldest soils. Thus, the proportion of the components in the clay assemblage, as well as their chemistry and interlayer charge, change over time with soil evolution.

Earlier interpretations of the conversion of the virgin smectite of the Ordovician Kinnekulle K-bentonites into the present mixed-layer illite/smectite imply that it took place through charge increase of the smectite with subsequent uptake and fixation of potassium. Recent analyses show that the layer charge of the smectite component of the I/S is in fact low and they suggest that neoformation of a separate illite phase took place. Pytte's kinetic model gives good agreement with the actual conversion rate for an activation energy of about 25–27 kcal/mole, depending on the adopted rate parameters, temperature history and assumed potassium source. In the Kinnekulle case the rate-controlling factor appears to have been the supply of potassium, which is concluded to have required large-scale, heat-induced groundwater convection.

The binary exchange of cations on clays and soils is generally regarded as a thermodynamically reversible process. The literature on soil chemistry and geochemistry, however, abounds with reports on cation exchange reactions that appear to have only limited reversibility, i.e., that exhibit hysteresis. A satisfactory explanation of this phenomenon is still lacking, even though a number of mechanisms have been advocated, e.g., charge or site heterogeneity at the surface, differential hydration of cations, dehydration of the exchanger, crystalline swelling hysteresis, and inaccessibility of sites caused by domain or quasi-crystal formation. In the present article, the relevant literature is reviewed and analyzed critically. On the basis of available evidence, it is shown that exchangeable cations can be classified into three groups, defined in such a way that hysteresis has, in the literature, generally not been observed when exchange reactions involved cations belonging to the same group, but has often been found when the reactions involved cations from different groups. Furthermore, it is argued that none of the five mechanisms mentioned can, in and of itself, account fully for the observed exchange hysteresis. A conceptual model is proposed that combines elements of these five mechanisms and is able to describe, at least qualitatively, the effects of factors such as clay type, electrolyte concentration, and extent of dehydration.

The structural transformation of dioctahedral 2:1 layer silicates (illite, montmorillonite, glauconite, and celadonite) during a dehydoxylation-rehydroxylation process has been studied by X-ray diffraction. thermal analysis, and infrared spectroscopy. The layers of the samples differ in the distribution of the octahedral cations over the cis- and trans-sites as determined by the analysis of the positions and intensities of the 11l, 02l reflections, and that of the relative displacements of adjacent layers along the a axis (c cos ß/a), as well as by dehydroxylation-temperature values. One illite, glauconite, and celadonite consist of trans-vacant (tv) layers; Wyoming montmorillonite is composed of cis-vacant (cv) layers, whereas in the other illite sample tv and cv layers are interstratified. The results obtained show that the rehydroxylated Al-rich minerals (montmorillonite, illites) consist of tv layers whatever the distribution of octahedral cations over cis- and trans-sites in the original structure. The reason for this is that in the dehydroxylated state, both tv and cv layers are transformed into the same layer structure where the former trans-sites are vacant.

The dehydroxylation of glauconite and celadonite is accompanied by a migration of the octahedral cations from former cis-octahedra to empty trans-sites. The structural transformation of these minerals during rehydroxylation depends probably on their cation composition. The rehydroxylation of celadonite preserves the octahedral-cation distribution formed after dehydroxylation. Therefore, most 2:1 layers of celadonite that rehydroxylate (~75%) have cis-vacant octahedra and, only in a minor part of the layers, a reverse cation migration from former trans-sites to empty octahedra occurred. In contrast, for a glauconite sample with a high content in IVA1 and VIAl the rehydroxylation is accompanied by the reverse cation migration and most of the 2:1 layers are transformed into tv layers.

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.

Reinterpretation of published data for shale cuttings from the Gulf of Mexico sedimentary basin identifies three reaction zones for illite formation with increasing depth for well CWRU6. In a shallow zone (1.85 to 3 km), non-expanding illite-like layers formed primarily by the coalescence of smectite 2:1 layers around interlayer K+. In a middle zone (3 to 4 km), illite crystals neoformed from solution as coarser K-bearing phases and smectite were dissolved by organic acids. In the deepest zone (>4 km), illite recrystallized as less stable illite crystals dissolved, and more stable illite crystals grew during mineral ripening. The progressive loss of radiogenic argon in the deepest zone yielded a constant apparent age for the clays with depth, an effect previously attributed to “punctuated diagenesis.” The above hypothesis for illite formation emphasizes the need to establish the zone (i.e., the reaction mechanism) from which shales were derived before making detailed geologic interpretations based on illite mineralogy.

The polyphenol theory of humic-substance formation has been studied extensively; however, an alternative theory, that humic substances are formed through the condensation of amino acids and reducing sugars (Maillard reaction), has not been explored to the same extent. The general objectives of this study were to determine whether smectites and goethites catalyze the abiotic polymerization of arginine and glucose to form humic-like compounds. The effects of smectite type, saturating cation, and the degree of Al substitution in goethites on the polymerization reaction were also studied. Four cation-saturated smectites and four Al-substituted goethites were incubated abiotically with solutions containing a mixture of arginine + glucose for 21 days at 37°C. After the incubations, total C recovered ranged from 80.6 to 123.8% and from 100.5 to 105.1% for the smectite and goethite systems, respectively. At the end of the incubations, 21.4–50.3% of the added C and 16.5–90% of the added N were sorbed on the various smectites, and 6.2–9.0% of the added C and 2.3–4.6% of added N was sorbed on the goethites in a form that could not be desorbed by washing with 100 mM CaCl2. X-ray diffraction analysis indicated that some of the sorbed C was intercalated in the smectites and FTIR analysis provided evidence of new absorption bands at 1650 and 1668 cm−1, which are consistent with Maillard reaction products. Thus, it is concluded that smectites catalyze the condensation of arginine and glucose to form humic-like products. Goethites, however, have little or no ability to catalyze this reaction.

The objective of the study was to contribute to the understanding of the influence of the structure and the 2:1 layer dimension of smectites on cation exchange capacity (CEC) reduction and the hydration behavior of Li-saturated smectites after heating. Five montmorillonites extracted from bentonites of different provenance were saturated with Li+ and heated to 300°C. Initial montmorillonites and montmorillonites with reduced layer charge (RCM) were characterized by comprehensive mineralogical analysis supplemented by CEC measurements, surface-area measurements by Ar adsorption, and 7Li, 27Al, and 29Si magic-angle spinning nuclear magnetic resonance spectroscopy (MAS NMR). The CEC of the initial montmorillonites varied between 89 and 130 cmol(+)/kg while the CEC of the RCM prepared at 300°C varied between 8 and 25 cmol(+)/kg. The lateral dimension of the 2:1 layers varied between 70 and 200 nm. The greatest decrease in CEC was observed for the montmorillonite with the largest diameter of the 2:1 layers and the smallest decrease was observed for the montmorillonite with the smallest diameter of the 2:1 layers. 7Li MAS NMR revealed an axially symmetric chemical environment of the hydrated interlayer Li+ with ηΔ = 0 for the chemical shift anisotropy tensor for unheated montmorillonites with >33% tetrahedral layer charge (ξ). The chemical environment is typical of innersphere hydration complexes of interlayer Li+. An axially non-symmetric chemical environment of the interlayer Li+ with ηCS of close to one was observed for all RCM. While the remaining CEC of RCM prepared at 300°C reflected the variable CEC at the edges, and thus the lateral size or aspect ratio of the 2:1 layers, the hydration complex of interlayer Li+ was strongly determined by the isomorphic substitutions in the dioctahedral 2:1 layers.

Atomic force microscopy (AFM) is a novel method for measuring changes in clay swelling in situ at the tactoid level in an aqueous environment. While the swelling process has been directly observed at the mesoscale level for multi-tactoid aggregates and the associated pores, no method to date has allowed the direct observation of swelling dynamics at the nanoscale. In initial proof-of-concept studies, individual tactoids of a Na-exchanged nontronite (NAu-1) were imaged in a solution of 5 mM NaCl. When multiple line profiles were examined on the same tactoid, the changes in height varied and depended on which layers of the profile were transected, and demonstrated that AFM analyses can be used to directly probe intratactoid heterogeneity in the swelling process. To better visualize this heterogeneity, a method was developed to restrict AFM images to include only the portions of a tactoid above a threshold height. A comparison of the changes in these images for multiple threshold values revealed that swelling in one part of a tactoid may occur simultaneously with compression in another portion, which suggests that the encroachment of layers into intra-tactoid micropores can partially compensate for the overall volume change. Finally, to demonstrate the ability of this technique to monitor in situ swelling changes as the surrounding aqueous environment is modified, a tactoid of K-montmorillonite (SWy-2) was monitored during cation exchange as a KCl solution was replaced with NaCl. After exchange, a transition from the crystalline swelling regime to the osmotic regime was observed. Subsequent height profiles were unchanged for a period of several hours and indicated that the AFM measurements were stable in the absence of changes to the aqueous phase composition. Because this technique is the first method that allows the swelling of a single tactoid to be monitored in an aqueous solution, it complements the ensemble-averaged data obtained from diffraction and scattering techniques.

The selectivities of clay minerals for larger organic cations over smaller ones have been attributed to favorable clay-organic interactions in clay interlayers and to hydrophobic effects resulting from (partial) dehydration of organic cations in the clay interlayers, but the magnitudes of these energy components have not been estimated. The objective of this study was to differentiate and quantify the contributions of clay-phase and aqueous-phase energy changes to the overall thermodynamics of cation exchange, and thereby to determine which forces control the general selectivity of smectites for organic cations. We compiled literature measurements and estimates for the free energies of overall cation exchange reactions and also for the free energies of organic cation hydration. Our study suggests that organic cation-exchange thermodynamics can be broken into three classes: (1) For two organic cations with identical head-groups, the difference in their cation exchange selectivities is driven almost quantitatively by the difference in their free energies of hydration. Here, the mechanism for organic cation selectivity is almost pure hydrophobic expulsion of the larger cation from water. The clay interlayer simply behaves like a subaqueous phase into which the least hydrophilic organic cations partition and the essentials of such cation exchange selectivity can be explained without any favorable clay-organic interactions. (2) For two organic cations with rather different head-groups, the difference in their cation exchange selectivities is just a small percentage of the difference in their free energies of hydration. This indicates that the clay phase interacts much more strongly with the cation having the smaller head-group, as might be expected on the basis of simple electrostatics. Here, the clay has an intrinsic strong preference for the cation with smaller head-group yet ‘selects’ for the cation with larger head-group because the aqueous-phase preference for the cation with smaller head-group is even stronger than the clay preference. (3) When the clay is already substantially loaded with organic cations, then van der Waals forces apparently can play a significant role in determining organic cation exchange selectivity differences.