The distributions of illite crystal (‘fundamental particle’) thickness in <0.2 µm fractions of 13 shale samples (from the Carpathian Foredeep, Poland), obtained using the Bertaut-Warren-Averbach X-ray diffraction method (MudMaster computer program), were analyzed and interpreted in terms of the mechanism of smectite illitization. All illite crystal thickness distributions in the analyzed shales are characterized by an ‘asymptotic’ shape. The origin of the asymptotic-type distributions is explained by the heterogeneity of illite crystals in shales, i.e. superposition of different populations of crystals, those included in illite-smectite (I-S) interstratifications, and those which occur as discrete illite. The analysis of the distributions in shales shows that the most frequent thickness class of illite crystals forming I-S is 2 nm. Discrete illite is composed of thicker crystals; though crystals as thin as 2 nm can also contribute to this population. The modeling of asymptotic distributions in shales by using a number of theoretical lognormal distributions shows that with progressive diagenesis, the mean thickness of illite crystals forming the I-S component increases gradually, whereas the discrete illite does not show a clear trend.

The diverse origins of illite crystals in shales do not permit determination of the mechanism of smectite illitization from the evolution of the shape of the overall crystal-thickness distribution during diagenesis. Therefore, in order to understand the mechanism of smectite illitization in shales, an attempt was made to trace the relative gains and losses of crystals of different thicknesses during illitization. This approach indicates the following mechanism of smectite illitization in the investigated shales: dissolution of smectite monolayers accompanied by growth of 2 nm crystals which are largely of detrital origin. Nucleation of 2 nm illites seems to be very limited.

The Li+ ion is used frequently as an environmentally acceptable surrogate for sorbing radionuclides in field tracer tests, and experiments using Li are an important part of assessing the potential transport of radionuclides in saturated alluvium south of Yucca Mountain, Nevada, the site of a proposed nuclear waste repository. Equilibrium partition constants (Li+ Kds) were measured using batch studies incorporating a wide range of Li+ concentrations and two different grain-size fractions of alluvium samples from multiple depth intervals in two wells. Cation exchange capacity, surface area, bulk mineralogy from quantitative X-ray powder diffraction, and trace Mn- and Fe-oxyhydroxide mineralogy from extractive studies were evaluated as predictors for linearized Li+ Kd values (K1in) in the alluvium. Many of the predictor variables are correlated with each other and this was considered in the analysis. Linearized Kd values were consistently higher for fine particle-size fractions than for coarse fractions. Single and multivariate linear regression analyses indicated that the clinoptilolite + smectite content, taken together as a combined variable, was the best predictor for Li+ sorption in the alluvium, although clinoptilolite content was clearly a better predictor when the two variables were considered separately in simple linear regressions. Even so, Li+ Klin predictions based on clinoptilolite and smectite abundance were accurate only to within about ±100%. This uncertainty suggests that there is either a high inherent variability in Li+ Klin values or that additional alluvium characteristics not measured or evaluated here may play an important role in simple Li+ cation exchange in the alluvium.

A new method for calculation of layer charge and charge distribution of smectites is proposed. The method is based on comparisons between X-ray diffraction (XRD) patterns of K-saturated, ethylene glycol-solvated, oriented samples and calculated XRD patterns for three-component, mixed-layer systems. For the calculated patterns it is assumed that the measured patterns can be modeled as random interstratifications of fully expanding 17.1 Å layers, partially expanding 13.5 Å layers and non-expanding 9.98 Å layers. The technique was tested using 29 well characterized smectites. According to their XRD patterns, smectites were classified as group 1 (low-charge smectites) and group 2 (high-charge smectites). The boundary between the two groups is at a layer charge of −0.46 equivalents per half unit-cell. Low-charge smectites are dominated by 17.1 Å layers, whereas high-charge smectites contain only 20% fully expandable layers on average. Smectite properties and industrial applications may be dictated by the proportion of 17.1 Å layers present. Non-expanding layers may control the behavior of smectites during weathering, facilitating the formation of illite layers after subsequent cycles of wetting and drying. The precision of the method is better than 3.5% at a layer charge of −0.50; therefore the method should be useful for basic research and for industrial purposes.

Nanostructural analysis of pillared clay samples using high-resolution transmission electron microscopy has been developed. Montmorillonite samples were pillared using partially hydrolyzed Al and Fe solutions. Two samples, M01 and M05, corresponding to Fe/(Fe+Al) ratios of 0.1 and 0.5, respectively, were analyzed. The different steps of image filtration, resulting from filtration by ring-shaped masks, are illustrated and discussed from lattice imaging of sample M01. This procedure is used to show the heterogeneous distribution of the basal spacings in the different ordered domains. Domains of mesoporosity and distribution of the different Fe species are studied specifically in the sample M05. The quantitative HRTEM results are discussed and compared with X-ray diffraction patterns obtained from the same sample.

Palygorskite-indigo and sepiolite-indigo adducts (2 wt.% indigo) were prepared by crushing the two compounds together in a mortar and heating the resulting mixtures at 150 and 120°C, respectively, for 20 h. The samples were tested chemically to ensure that they displayed the characteristic properties of Maya Blue. Textural analysis revealed that no apparent changes in microporosity occurred in sepiolite or palygorskite after thermal treatment at 120°C (sepiolite) and 150°C (palygorskite) for 20 h. Micropore measurements showed a loss of microporosity in both sepiolite and palygorskite after reaction with indigo. The TGA-DTG curves of the sepiolite-indigo and palygorskite-indigo adducts were similar to their pure clay mineral counterparts except for an additional weight loss at ∼360°C due to indigo.

The 29Si CP/MAS-NMR spectrum of the heated sepiolite-indigo adduct is very reminiscent of the spectrum of dehydrated sepiolite. Crushing indigo and sepiolite together initiates a complexation, clearly seen in the 13C CP/MAS-NMR spectrum, which can be driven to completion by heat application. In contrast to the broad peaks of the pure indigo 13C CP/MAS-NMR spectrum, the sepiolite-indigo adduct spectrum consists of a well-defined series of six narrow peaks in the 120.0–125.0 ppm range. In addition, the sepiolite-indigo spectrum has two narrow, shifted peaks corresponding to the carbonyl group and the C-7 (C-16) of indigo. A model is proposed in which indigo molecules are rigidly fixed to the clay mineral surface through hydrogen bonds with edge silanol groups, and these molecules act to block the nano-tunnel entrances.

The effects of a subvolcanic intrusion on its host rocks in the Priego de Córdoba area (SE Spain) was studied by optical microscopy, X-ray diffraction and electron microscopy. The intrusion of a laccolith of stratiform dolerite in partially consolidated marly sediments at quite shallow depths below the ocean floor took place during the intracontinental rifting phase of the Subbetic zone of the Betic Cordilleras. In the first stage, contact metamorphism caused the crystallization of calc-silicate consisting of grossular andradite garnet, diopside, vesuvianite and titanite for which the upper temperature limit was 500°C. Phyllosilicates are found in a network of veins cross-cutting the carbonate and calc-silicate matrix, indicating their formation during a process of hydrothermal alteration superimposed on the contact aureole. In the area closest to the subvolcanic rocks, saponite is the main phyllosilicate although some dispersed chlorite is found. In the zone furthest from the contact, corrensite together with saponite and beidellitic smectites were observed. The presence of low-temperature phases (saponite) in the area closest to the laccolith reveals the evolution of the hydrothermal system toward cooler conditions. In the early stage, the circulation of a hot hydrothermal fluid caused the crystallization of chlorite in the area surrounding the subvolcanic body and corrensite in the more distal area, which might have begun even during the contact metamorphism stage. A cooling phase followed, resulting in the crystallization of saponite in the host rocks, and the crystallization of dioctahedral and trioctahedral smectites inside the subvolcanic body.

Hybrid Langmuir-Blodgett (LB) films of a single clay layer and a donor-(π-electron system)-acceptor (Dδ-π-Aδ−) zwitterionic molecule (ind-TCNQ), prepared from 1,3,3-trimethyl-2-methyleneindoline (donor) and 7,7,8,8-tetracyanoquinodimethane (acceptor) were prepared. The characteristics of the electrostatic interaction between the clay layer and the ind-TCNQ molecules were investigated. The amount of ind-TCNQ molecules spread onto the air-water interface was increased systematically so that mono- and multi-layers of the molecules could be formed on the clay layer. The hybrid LB films, which were deposited onto a solid substrate, were characterized by means of UV-vis absorption spectroscopy and optical second-harmonic generation measurement. The amount of ind-TCNQ molecules adsorbed on the clay layer increased with an increase in the amount of ind-TCNQ molecules spread onto the air-water interface. On the other hand, the SHG intensities of the films did not change with the change in amount of ind-TCNQ spread. The results indicate that the electrostatic interaction between the clay layer and the ind-TCNQ molecules operates only in the region where the ind-TCNQ molecules are in direct contact with the clay layer.

The effect of humic acid (HA) adsorption on the hydrophilicity of two different montmorillonite samples (Na-montmorillonite, NaMt, and a Na-fluorinated Na-montmorillonite, FNaMt, or ‘Rassoul’) was investigated. The changes in the wettability of clays were discussed in terms of the non-electrostatic free energy of interaction between the clay particles immersed in aqueous humic acid solutions (ΔG121), using the van Oss-Chaudhury-Good (vOCG) model. The surface free energy components (both non-polar or Lifshitz-van der Waals, and polar or acid-base) of clays were obtained from contact angle measurements, after adsorption of humic acid, at acid or basic pH, in 10−2 M NaCl solutions. It was found that: (1) at acid pH, a progressive decrease in the hydrophilic character of both clays was observed when the humic acid concentration was increased; (2) at basic pH, the hydrophilic character of both samples studied increased with HA concentration; (3) the effect of humic acid adsorption on the wettability of model edge surfaces of the laminar montmorillonite particles was estimated from a parallel study on silica and alumina surfaces, and only a slight decrease in the hydrophilicity was observed, whatever the pH of the liquid media. The ζ potentials of both clays in the absence and presence of humic acid were determined and the linkage between ζ potential and the electron-donor character of the materials is discussed.

The influence of cation size on the misfit between the tetrahedral and the octahedral sheets of serpentine layers, and thus on the curvature of serpentine minerals, has been studied using an experimental approach, based on scanning and high-resolution transmission electron microscopies (SEM and HRTEM, respectively) coupled with analytical electron microscopy (AEM), and a theoretical approach, based on the elastic theory of thin plates and the surface stress concept.

Various Ni3(Si,Ge)2O5(OH)4 serpentine syntheses were prepared, with progressive tetrahedral substitution for Si by the larger Ge ion, the ratio Ge/(Si + Ge) ranging from 0 to 100%. Other parameters (temperature, time duration, water pressure) were fixed. From SEM-HRTEM observations and AEM analyses of all samples, two types of serpentine minerals were characterized: (1) curved structures of tubular or ‘roman-tile’ shape (curvature radius of 10 nm for 0% Ge, increasing with the Ge content), when the Ge tetrahedral content is <25%; (2) perfectly plane structures, with hexagonal or triangular shape (view normal to the layers), for greater Ge contents. These results prove the direct influence of cation size on the crystal curvature.

From a theoretical point of view, a single serpentine layer with a misfit between its tetrahedral and octahedral sheets can be considered as an elastic thin plate subjected to two different surface stresses, σ+ and σ−, on its two faces. The difference σ+ − σ− between these two surface stresses was calculated from the above geometrical misfit, and the curvature of the serpentine layer was related to σ+ − σ−, according to the elastic theory of thin plates. The calculated curvature radii, and the Ge content of transition from curved to plane structures, are in agreement with the above observed values. Curved serpentine crystals may then be considered as a stacking of such elastically curved single serpentine layers.

The results of a combined chemico-osmotic/diffusion experiment conducted on a geosynthetic clay liner (GCL) containing Na-bentonite illustrate the destructive role of diffusion on the ability of the GCL to act as a semipermeable membrane. The experiment is conducted by maintaining a concentration difference of 5 mM CaCl2 across the GCL specimen while preventing the flow of solution through the specimen. A time-dependent membrane efficiency is derived from measured pressure differences induced across the specimen in response to the applied concentration difference. The diffusive mass fluxes of the solutes (Cl− and Ca2+) through the specimen are also measured simultaneously. An initial increase in induced pressure difference across the specimen to a peak value of 19.3 kPa is observed, followed by a gradual decrease to zero. The decrease in induced pressure difference is consistent with compression of diffuse double layers between clay particles and particle clusters due to diffusion of Ca2+, resulting in a concomitant increase in pore sizes and decrease in the observed membrane behavior. The time required for effective destruction of the initially observed semipermeable membrane behavior correlates well with the time required to achieve steady-state Ca2+ diffusion. The results have important implications for the ability of clays to sustain membrane behavior.

Octadecylamine (ODA) was used to intercalate a fine-grained and a coarse-grained fraction of natural Mg-vermiculite (VER) using a low-temperature melting procedure. Mixtures of Mg-vermiculite fractions and powdered ODA in the molar ratios of 2:1, 1:1, 1:2 and 1:6 were homogenized and heated for 1, 3, 15 and 30 h at 80°C to prepare intercalated samples. X-ray powder diffraction analysis of intercalated samples was combined with molecular modeling to investigate their interlayer structure. Significant amounts of non-intercalated vermiculite and diffuse peaks with very low intensity and basal spacings close to 29 Å were identified when the lowest concentration (molar ratio VER:ODA = 2:1) was used. According to molecular modeling, this indicates the initial stage of a one-layer arrangement of distorted ODA molecules in the interlayer. If the concentration of ODA molecules and treatment time were increased, a two-layer arrangement of ODA molecules with a different ODA chain-disorder and interlayer-space saturation was identified. Interlayer ODA molecules were inclined to the vermiculite basal plane with an inclination angle for two-layer arrangements that ranged from 76 to 95°. Experimental basal spacings with these two-layer arrangements varied from 52 to 58 Å and were in agreement with molecular modeling results. A fully-saturated 58 Å two-layer ODA arrangement was identified when higher ODA concentrations (VER:ODA = 1:2 and 1:6) and 15 and 30 h treatment times were used. There was no significant difference between ODA-intercalated samples prepared using fine-grained and coarse-grained Mg-vermiculite fractions. A grafted ODA-chain nano-layer with a 49.6(2.1) Å average height was observed on the surface of thin ODA-intercalated micro-flakes using atomic force microscopy. Grafted ODA chains not only created an homogeneous surface nano-layer, but also variable-width channels between the ODA molecules.

The mechanism of decolorization of crude maize and sunflower oils was studied by means of adsorption of β-carotene by a low-grade bentonite, containing mixed-layered illite-smectite. Decolorization depends on temperature and the time required for equilibrium decreases with increasing temperature. The study of the kinetics of adsorption showed that decolorization of maize oil is a first-order process which occurs in two steps: a first fast step with higher activation energy (25.6 kJ mol−1), indicating the influence of a chemical interaction between the pigment and the clay surface, followed by a second slow step with low activation energy (12.3 kJ mol−1), characteristic of physical adsorption on the previously adsorbed molecules. Decolorization of sunflower oil is also a first-order process, described by a single mechanism with intermediate activation energy (19.0 kJ mol−1). Adsorption isotherms of decolorization of maize oil follow the Freundlich equation, indicating the existence of heterogeneous adsorption sites on the solid's surface. Heterogeneity is attributed both to different active centers on the smectite surface (Brönsted and Lewis centers) and to the different phases present in bentonite, such as illitic layers and clinoptilolite, which also have active centers on their surfaces.

The loss of K-bearing clay minerals has been observed over an 80 y cultivation period in Chinese rice paddies despite the use of NKP fertilizers. Clay mineral determinations were made in flood-irrigated paddies cultivated for 3, 10, 15, 30 and 80 y in clayey (45 wt.%), red soils derived from red Quaternary sediments. Three clay minerals are initially present in these soils: illite-mica, magnesian chlorite and an interstratified mica-aluminous chlorite mineral. This last phase was identified using computer simulations. The K-bearing phases (discrete mica and illite as well as interstratified mica layers) are to a large extent lost while the Fe content decreases in the soil as a whole and increases in the chlorite. The mica component in the mixed-layer mineral decreases also. These changes in clay mineralogy and relative abundance suggest a loss of potassic minerals and an increase in the formation of less siliceous, more ferro-magnesian chlorite. These changes occur over 30 y or less, a rather rapid, irreversible transformation of soil clay minerals. Such loss of potassic minerals renders the cultivation more dependent on fertilizer amendment.

The rheological characteristics of purified bentonite suspensions as a function of exchangeable cation $({\text{Ca}}^{2+},{\text{NH}}_4^{+},{\text{Li}}^{+})$$({\rm{C}}{{\rm{a}}^{2 + }},{\rm{NH}}_4^ + ,\;{\rm{L}}{{\rm{i}}^ + })$ are studied at three different clay concentrations (40 gL−1, 60 gL−1, 80 gL−1). A Herschel-Bulkley model is used to determine rheological parameters such as yield value, consistency and fluidification index. The flow curves are typical for shear thinning fluids but differ on two points; presence of yield stress and/or thixotropy. The Li suspensions are not yield stress fluid, and the thixotropy is weakly expressed only for the 80 gL−1 suspension. On the contrary, Ca-clay suspension flow curves always present yield stress and a large thixotropic area. The NH4-clay suspensions exhibit an intermediate behavior as there is no thixotropy, but a yield stress appears for the most concentrated suspension. These differences in macroscopic mechanical properties are discussed with reference to the suggested microscopic clay organization in suspension.

Rb-Sr and oxygen isotope studies, in addition to K-Ar isotopic determinations published previously, are reported on diagenetic and hydrothermal fundamental particles (particle thickness of 0.03 to 0.05 nm and particle ab size of 0.02–0.05 µm) of the East-Slovak Basin. The combined data set allows us to ascertain the crystallization conditions of the illite material from two bentonite units collected at two basinal sites located ~20 km apart, and characterized by prolonged diagenetic conditions induced by progressive burial. A bentonite rock characterized by a short hydrothermal event from the Zempleni mountains to the SW of the East-Slovak basin is also studied.

For the two first sites, the δ18O values increase in one case and decrease in the other, when the size of the diagenetic fundamental particles from bentonite samples increases. These variations suggest that temperature increased in one and decreased in the second of the two samples collected in the basin, while the particles were growing. In the case of the hydrothermal bentonite, the δ18O values of the different size-fractions consisting of fundamental particles remain about constant, suggesting constant temperature and fluid chemistry.

The Rb-Sr dates of the fundamental particles of the three bentonite rocks were systematically higher than the corresponding K-Ar ages. The 87Sr/86Sr ratios, which are initially involved in the particle nucleation, appeared higher than that of contemporaneous sea-water. In all cases, the initial 87Sr/ 86Sr ratio decreases when particle size increases, which implies supply of external Sr into the bentonite units. This external Sr seems to have had an 87Sr/86Sr ratio close or identical to that of the contemporaneous sea water. This means that Sr, probably of sea-water origin, progressively diffused from host shales into the bentonite units, during burial diagenesis. In turn it favors the suggestion made previously about diffusion of K from shales into the bentonite layers during illitization of the smectite from these units.

The As sorption capacity of a natural Mn and Fe mineral-containing sample from the Iron Quadrangle province, Brazil, was investigated. A detailed mineralogical identification was obtained by combining X-ray diffraction analyses (with Rietveld refinement), X-ray fluorescence spectroscopy, optical microscopy, and scanning electron microscopy coupled with X-ray energy dispersive spectrometry-EDS. The oxidation state of the adsorbed As species was determined by X-ray absorption near edge structure spectroscopy. The results demonstrate that the presence of naturally occurring Mn oxides promotes the effective oxidation of As (III) to As(V). Also, the Mn minerals show a significant uptake of both the trivalent and pentavalent As species. This study demonstrates that the combined influences of As(III) depletion by oxidation and adsorption on a natural oxide sample consisting of Mn minerals and Fe oxides may effectively contribute to the reduction the As concentration in waters.

The formation of siderite and magnetite by Fe(III)-reducing bacteria may play an important role in C and Fe geochemistry in subsurface and ocean sediments. The objective of this study was to identify environmental factors that control the formation of siderite (FeCO3) and magnetite (Fe3O4) by Fe(III)-reducing bacteria. Psychrotolerant (<20°C), mesophilic (20–35°C) and thermophilic (>45°C) Fe(III)-reducing bacteria were used to examine the reduction of a poorly crystalline iron oxide, akaganeite (β-FeOOH), without a soluble electron shuttle, anthraquinone disulfuonate (AQDS), in the presence of N2, N2-CO2(80:20, V:V), H2 and H2-CO2 (80:20, V:V) headspace gases as well as in -buffered medium (30–210 mM) under a N2 atmosphere. Iron biomineralization was also examined under different growth conditions such as salinity, pH, incubation time, incubation temperature and electron donors. Magnetite formation was dominant under a N2 and a H2 atmosphere. Siderite formation was dominant under a H2-CO2 atmosphere. A mixture of magnetite and siderite was formed in the presence of a N2-CO2 headspace. Akaganeite was reduced and transformed to siderite and magnetite in a -buffered medium (>120 mM) with lactate as an electron donor in the presence of a N2 atmosphere. Biogeochemical and environmental factors controlling the phases of the secondary mineral suite include medium pH, salinity, electron donors, atmospheric composition and incubation time. These results indicate that microbial Fe(III) reduction may play an important role in Fe and C biogeochemistry as well as C sequestration in natural environments.

Hydrotalcite-like layered double hydroxides (LDHs) containing different ratios of Ni2+, Cu2+, Mg2+ and Al3+ in the layers have been prepared by a new method, the key features of which are a very rapid mixing and nucleation process in a colloid mill followed by a separate ageing process. The compositions and structural parameters of the materials synthesized using the two routes are very similar, although the degree of crystallinity is slightly higher for the LDHs produced using the new method. The major advantage of the new method is that it produces smaller crystallites, having a very narrow range of distribution of crystallite size. In the conventional coprecipitation process at constant pH, the mixing process takes a considerable time during which nuclei formed at the beginning of the process have a much longer time to undergo crystal growth than those formed at the end of the process. The consequence is that a wide dispersion of crystallite sizes is obtained. In the colloid mill process, however, the mixing and nucleation is complete in a very short time and is followed by a separate ageing process.

We report infrared spectroscopic observations of the incorporation of CO2 into pyrophyllite that has been heated between 200°C and 1250°C for periods of 15 min, 1 h and 5 days. The presence of CO2 is characterized by the ν3 band of CO2 near 2347 cm−1, detectable in samples in which dehydroxylation has commenced after heating above 450°C. With increasing temperature, the CO2 signal becomes more intense. The signal reaches its maximum intensity near 800°C with an annealing time of 15 min. Further heating leads to a decrease in the CO2 signal and the occurrence of an extra signal near 2156 cm−1 that implies the presence of CO. The process is characterized by significant time-dependence, indicating its kinetic nature. The peak positions of CO2 signals show systematic variations with temperature. Our results suggest that the CO2 molecule is associated with the local structure rather than being present as free gaseous CO2, and that the local structure of pyrophyllite is gradually modified during high-temperature treatments. However, no signals related to carbonate molecules ($({\text{CO}}_3^{2-})$) were detected. The results suggest that CO2 or other carbon-based molecules may diffuse into some clay minerals during dehydroxylation and may become altered due to structural modifications at high temperatures. This may have significance for possible CO2 sequestration in shales and clay formations.

The mechanism by which the anionic polymers interact with platelets of 2:1 clay minerals is not fully understood. The objective of the present study was to evaluate the effect of the electric field associated with the basal and edge surfaces of the clay minerals on the adsorption of anionic polymers. Two negatively charged polymers, PAM90 and ACC86, of the same molecular weig ht (2 × 105 g mol−1) but with different degrees of hydrolysis (90 and 20%, respectively), were used. The effect of pH (6, 10), NaCl concentration (0, 10 mmolC L−1) and clay particle size on PAM90 adsorption by pyrophyllite and the effect of NaCl concentration on the adsorption of these polymers by Na-montmorillonite in aqueous suspensions were studied. Adsorption of PAM90 on pyrophyllite was greater at pH 6 than at pH 10 and greater in 10 mmol L−1 NaCl than in distilled water. Adsorption of PAM90 on pyrophyllite increased with decreasing particle size. On pyrophyllite the high-charge-density PAM90 was adsorbed to a greater extent than the low-charge-density ACC86; by contrast, ACC86 adsorption was greater than that of PAM90 on Na-montmorillonite. These results were attributed to the repulsive forces which develop between the negatively charged extended-chain polymer and the extended negative electric field associated with the basal surfaces, around the Na-montmorillonite platelets. The results may suggest that the edge surfaces play a major role in PAM adsorption.