Self-diffusion coefficients of H2O molecules in water-rich gels of Na-rich expandable mica synthesized using natural talc were measured by pulsed-gradient spin-echo 1H nuclear magnetic resonance (NMR), and the dependence on mica fraction (0.00–43.8 wt.%) and temperature (30.0–60.9°C) was examined. On the basis of the NMR results, the self-diffusion coefficient of H2O, Dwater, in the gel can be expressed by ln(Dwater/D0water) = 1.64[exp( −0.0588w) - 1], where D0water is the self-diffusivity of bulk water at temperature and w is the weight fraction of the mica (wt.%). The activation energy of H2O diffusivity in mica gel is nearly equal to that in bulk water. These findings indicate that the normalized diffusivity, Dwater/D0water, is independent of temperature. The diffusivity of I−, Diodine, in the gels was examined by X-ray computed tomography (CT) at 22°C, and the influence of the mica fraction (0.00–24.8 wt.%) was studied to determine the contribution of bound H2O. The X-ray CT results show that the normalized I− diffusivity, Diodine/D0iodine, obeys the above-mentioned phenomenological curve where D0iodine is the I− diffusivity in bulk water. I− is non-sorbing, and thus its diffusion is restricted only by the geometrical complexity of the pore structure of gels. Therefore, the effect of bound H2O molecules on average H2O diffusivity is negligible for w <24.8 wt.%. Diffusivity is governed by free or unbound H2O molecules diffusing in the geometrically complex and tortuous pore structure of mica-mineral grains. This is a result of the large population of unbound H2O far from the grain surface compared to the small population of bound H2O near the grain surface. The diffusion of I− ions in montmorillonite gels was examined by X-ray CT for w <16.7 wt.% montmorillonite. The normalized iodine diffusivity, (Diodine/D0iodine) obtained is in reasonably close agreement with the literature data for the normalized diffusivity of H2O and is similar to the master curve of expandable mica. Therefore, bound H2O molecules near negatively charged clay surfaces do not play a major role in the H2O diffusivity for water-rich montmorillonite gels.

A low-charge Na-montmorillonite (SWy-2) was exchanged with hexadecyltrimethyl-ammonium (HDTMA) at levels equal to 20, 40, 60, 70, 80, 90, 100, 150 and 200% of the cation exchange capacity (819 mmol(+)/kg) to determine the nature of adsorption and the ionic composition of the clay interlayers. In contrast with earlier work with smaller aliphatic cations, which suggested random interstratification of interlayers occupied by either organic or metallic cations, there was no evidence of cation segregation into homogeneous interlayers. Instead, X-ray analysis indicated that the organic cations assumed two dominant configurations which were roughly equivalent in prevalence at ∼70% coverage of the CEC. Below 70% exchange the organocations existed predominantly in heterogeneous monolayers with Na+, attaining basal spacings of between 1.41 and 1.44 nm which were sensitive to changes in relative humidity. Relative humidity effects indicated that Na+ and HDTMA occupied functionally discrete domains within the interlayer as shown by the free interaction of water and a neutral organic solute, naphthalene, with Na+ and HDTMA, respectively. At greater levels of HDTMA exchange (up to 100% of the CEC), the organocations assumed a predominantly bilayer configuration. Transition to a fully-developed bilayer indicated by a 1.77 nm d-spacing at 100% coverage was gradual, suggesting some interstratification of the monolayers and bilayer configurations between 70 and 100% exchange. Sorption of naphthalene to the organoclays within this range of coverage was well correlated with clay organic carbon content, consistent with relatively unimpeded interlayer access of neutral organic molecules.

Quasicrystals of synthetic fluoromagnesian smectite (FMS) in dodecyltrimethylammonium chloride (DTAC) solutions were investigated as a function of the DTAC concentration by wet type X-ray diffraction (XRD) ζ potential measurements, and dispersion and coagulation (DC) tests. The FMS had an electronegative potential and it was dispersed randomly in an aqueous suspension without DTAC. When the DTAC concentration was 0.002 mol/dm3, FMS tactoids started to develop a structure in which the layer thickness was 1.85 nm. At the isoelectric point, the DTAC concentration was 0.012 mol/dm3 and the FMS tactoid formed a regular stacked structure with a 2.25 nm layer thickness. As the ζ potential of FMS changed from negative to positive, the DC test and XRD measurement showed that the FMS association gradually changed from coagulation to dispersion, which indicates that the formation of the bilayer of surfactants on the surface of FMS produces a repulsion between DTA+ adsorbed on the silicate layer of the FMS surfaces. When the equilibrium concentration of DTAC in solution exceeded the critical micelle concentration (CMC), the ζ potential of FMS became greater than the previous values. The XRD analysis of this suspension showed that there were two kinds of rational FMS stackings; one has a layer thickness of 3.20 nm, and the other has a layer thickness of 5.45 nm due to an interstratified structure composed of 3.20 and 2.25 nm layers. The interstratified structure was confirmed by the calculated XRD profiles.

The adsorption of two dinitrophenol herbicides, 4,6-dinitro-o-cresol (DNOC) and 4,6-dinitro-o-sec-butyl phenol (dinoseb), by two reference smectite clays (SWy-2 and SAz-1) was evaluated using a combination of sorption isotherms, Fourier transformation infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and molecular dynamic simulations. Clays were subject to saturation with various cations, and charge reduction. The DNOC adsorption decreased with increasing pH indicating that DNOC was primarily adsorbed as the neutral species. The FTIR spectra of DNOC-clay films showed that DNOC molecules are oriented parallel to the clay surface. Interlayer cations have a strong effect on adsorption depending largely on their hydration energies. Weakly hydrated cations, e.g. K+ and Cs+, resulted in greater sorption compared to more strongly hydrated cations such as Na+ or Ca2+. Lower hydration favors direct interactions of exchangeable cations with -NO2 groups of DNOC and manifests optimal interlayer spacings for adsorption. In the presence of sorbed DNOC, an interlayer spacing for K-SWy-2 of between 12 and 12.5 Å was maintained regardless of the presence of water. This d-spacing allowed DNOC molecules to interact simultaneously with the opposing clay layers thus minimizing contact of DNOC with water. The charge density of clays also affected sorption by controlling the size of adsorption domains. Accordingly, DNOC adsorption by low-charge clay (K-SWy-2) was much higher than by high-charge clay (K-SAz-1) and Li-charge reduction greatly enhanced dinoseb adsorption by K-SAz-1. Steric constraints were also evident from the observation that adsorption of DNOC, which contains a methyl substituent, was much greater than dinoseb, which contains a bulkier isobutyl group. Adsorption of DNOC by K-SAz-1 was not affected in the presence of dinoseb, whereas dinoseb adsorption was greatly reduced in the presence of DNOC.

The effect of heavy doses (up to 200 Mrad) of γ-radiation on the short-range structural organization in montmorillonite was studied using infrared (IR) spectroscopy and solid-state high-resolution 27Al and 29Si nuclear magnetic resonance (NMR). No change attributable to irradiation was observed. A small variation in the water content was noted but it is not systematic. The results show that the montmorillonite structure can accumulate high doses of radiation without damage and therefore this clay is a suitable material for use in the safe disposal of radioactive waste.

The fluoride ion is crystal chemically very similar to the hydroxyl ion, substituting for hydroxyl in many minerals in which hydrogen bonding is not important. Fluoride substitutions are particularly common in 2:1 layer silicates, such as micas, illites and smectites. The brick and tile industries, which use naturally occurring clays as their primary raw materials, have devoted considerable effort to understanding fluorine evolution during firing of the raw materials due to increasingly stringent fluorine emission regulations. In order to understand fluorine evolution from ceramic raw materials, we have studied a number of phyllosilicate materials used in making bricks. X-ray powder diffraction and fluorine analyses were combined with heating experiments and thermogravimetric analysis to evaluate the chemical and structural changes taking place on heating. Fluorine remained in 2:1 layer silicates to higher temperatures than did hydroxyl, but it behaved identically to hydroxyl in the kaolinite studied. In all cases, fluorine evolution coincided with structural breakdown of the clay host. These results show that fluorine evolution will consistently occur during firing of clay raw materials, and the problems of fluorine emission cannot be readily solved by simple variations of firing temperatures or times.

The intercalation complex of a kaolinite from Cornwall, UK, with dimethylsulfoxide (DMSO) was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA) and thermogravimetry (TG). The X-ray pattern obtained at room temperature indicated that intercalation of DMSO into kaolinite caused an increase of the basal spacing of kaolinite from 7.14 to 11.19 Å. Heating between 25 and 300°C caused the removal of the DMSO, which occurred over several stages. In a first stage (25–125°C), an expansion (from 11.19 to 11.28 Å) followed by a contraction (from 11.28 to 11.19 Å) is observed, at the same time as the intensity of the basal reflection decreased and was replaced by a broad band extending from ~11 to ~7 Å. In a second stage (125–200°C), the loss of DMSO did not lead to changes in the HTXRD patterns; and finally, in a third stage, the loss of DMSO caused an important increase in intensity and sharpening of the basal reflections of the kaolinite. These stages were also shown by the DTA-TG curves for the complex. The TG curve indicated that the loss of ~15% of the intercalated DMSO occurs below 150°C, and caused the disruption of the structure. The remaining molecules, forming stronger bonds with the kaolinite surfaces, were lost between 150 and 300°C.

Polarized micro-Raman spectra of a single large crystal of Keokuk kaolinite were recorded in the OH-stretching region with the laser beam directed along the different crystal axes. The Raman spectra are characterized by five OH-stretching bands at 3694, 3683, 3668, 3650 and 3620 cm−1 labeled A, Z, B, C and D, respectively. The relative intensities of these five bands depend on the orientation of the crystal and the scattering geometry. The spectra agree with the assertion that bands A and Z arise from out-of-plane vibrations, whereas band D corresponds to an in-plane vibration. The area ratios of the various bands were calculated from fitted curves of spectra recorded with the electric vector of the laser beam parallel to different crystallographic planes. The increments in the relative areas of bands B and C were parallel to those of bands A and Z and it appears that out-of-plane vibrations made considerable contributions to these bands also. From the change of area ratios with the change in the direction of the electric vector of the laser beam, bands A and Z were attributed to LO and TO frequencies of one inner-surface hydroxyl vibration. Bands A + Z, B, C and D were attributed to the vibrations of the hydroxyls assigned by Bish (1993) as OH(3), OH(4), OH(2) and OH(1), respectively. These observations were supported by photoacoustic and transmission IR spectra.

Birnessite can be used as a precursor in the preparation of manganese oxides. Synthesis of pure birnessite is difficult because of a side reaction, which yields hausmannite. This study aimed to develop a modified oxidation-deprotonation reaction (ODPR) method to eliminate the formation of hausmannite, and to investigate the influence of alkalinity on the synthetic products. In contrast to the conventional synthesis of birnessite through oxygen or permanganate oxidation, the ODPR method can produce birnessite without any impurities, within 5 h, and in a reproducible fashion. The distinctive feature of the ODPR method is the bubbling of N2 gas into NaOH and Mn2+ solutions before mixing the NaOH with Mn2+, in order to keep oxygen away from each solution. As soon as white pyrochroite was formed, oxygen gas was forced in as an oxidant to initiate the oxidation reaction. A black suspension with a blue tint appeared after 5 h of reaction. These precipitates were collected and examined by X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared (IR) and Raman spectroscopy. The average oxidation state of the Mn oxides was also determined. The results showed that pure birnessite with good crystallinity was formed. Oxidation of 1 M NaOH mixed with Mn2+ solution formed random-stacked birnessite. However, the oxidation of 4 M NaOH mixed with Mn2+ formed birnessite. Random-stacked birnessite can be transformed into birnessite by ageing suspensions at 313 to 373 K.

Sudoites exhibit different crystal-chemical and textural properties which may be related to the structural and valence state of Fe. Mössbauer spectroscopic analysis shows that all Fe previously analyzed using a microprobe (from 1 wt.% to 7.2 wt.% total Fe as Fe2O3) is structural and occurs in both oxidation states (40% Fe2+ and ∼60% Fe3+). Electron microprobe analyses from ∼200 sudoites indicate that Fe occurs in both octahedral sheets according to three main types of substitution: Fe3+ = octahedral Al; Fe2+ = Mg; and Fe3+ + Fe2++ □ = 3Mg. Decreasing tetrahedral substitution balances Fe3+ substitution in the trioctahedral sheet. Increasing octahedral Fe results in a more dioctahedral character of sudoite.

X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis (DTA) and scanning electron microscope-transmission electron microscope (SEM-TEM) analyses showed that increasing octahedral Fe is associated with decreased stacking order and thermal stability due to the greater number of defects. In addition, with increasing octahedral Fe in sudoite, particles became smaller and more anhedral and consequently less stable with increasing Fe content. These structural and textural variations are interpreted as a result of the distortion of the sudoite structure by substitutions of Fe3+ with larger ionic radii for Al and Mg octahedral cations and by the formation of octahedral vacancies.

Illite-smectite (I-S) minerals isolated from Upper Jurassic oil-source rock shales from Denmark and the North Sea have been investigated by X-ray diffraction, thermal analysis, infrared, Mössbauer, and solid-state nuclear magnetic resonance spectroscopies and chemical analysis. Detailed structures have been determined in order to reveal the diagenetic transformation mechanism in these shales. Generally, in oil-source rocks of sedimentary basins, oil generation takes place simultaneously with the diagenetic transformation of I-S. We demonstrate a link between the two reactions: NH3 released from kerogen during maximum oil generation is fixed as NH4+ in the NH4-bearing mica or tobelite layers formed from smectite or vermiculite layers in I-S, in a diagenetic interval which we name the ‘tobelitization window’. Due to this solid-state transformation, mixed-layer structures have been formed consisting of interstratified illite, tobelite, smectite and vermiculite layers (I-T-S-V) and having maximum ordering of illite + tobelite and smectite layers for R = 1. The tobelitization of smectite in I-S is probably typical for all oil-source rock shales.

Bacterial mineralization in weathered pyroclastic deposits of the Kaimondake volcanic ash (4040 ybp) and the Koya pyroclastic flow (6400 ybp) was investigated to evaluate the impacts of bacteria on mineral formation, and to characterize the microbiogenic minerals in the weathering environment. The mineralogy of abiogenic weathering products was also investigated for comparison with the microbiogenic products, and mineral saturation indices were calculated for porewaters using the PHREEQC computer code. The results indicated that these weathered pyroclastic deposits contain 108–109 cells/g, consisting of spherical to rod-shaped bacteria. Associated abiogenic allophane had an Al/Si ratio ranging from 1.01 to 2.13. The bacterial cell surfaces were completely or partially covered by poorly-ordered silicate minerals, which could be divided into two groups based on their chemical and morphological characteristics. Group I was characterized by well developed fibrous to smectite-like flaky habits with variable Al, Si and Fe, corresponding to compositions between proto-imogolite allophane and chamosite. These Al-Si-Fe minerals were the most abundant and major microbiogenic products in both lithologies. Group II exhibited poorly-developed aggregates of allophane-like granular materials composed mainly of Al and Si with minor Fe. Geochemical calculations revealed that the porewaters were saturated with respect to allophane and other crystalline clay minerals such as halloysite, kaolinite, montmorillonite and nontronite. These microbiogenic minerals may be formed as the earliest phase of these clay minerals after interaction of the bacterial cell surfaces with dissolved cations mainly Si, Al and Fe, in the porewaters.

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.

Clinoptilolite-rich materials from widespread pyroclastic and epiclastic deposits of northern Sardinia were investigated to assess their cation exchange properties and to find the most reliable experimental method to determine their cation exchange capacity (CEC). The CECs were evaluated using a cross exchange method (CEM) and a batch exchange method (BEM). The CEM resulted in values 30–35% lower than the theoretical or expected CEC calculated from the chemical analyses of the clinoptilolite-rich materials. The BEM resulted in CECs 6–12% lower than the expected CECs. Various parameters, such as the grain-size of powders (<64 µm and 125–250 µm) and replacement cation (Na+, K+, Li+, Cs+, NH4+, Ca2+, Mg2+, Sr2+) were evaluated in order to optimize the cation exchange process, i.e. enhance complete exchange. The particle size did not affect the exchange process appreciably. The type of replacement cation had a substantial effect on the experimental CEC determined by the BEM. The NH4+ and Cs+ replacement solutions resulted in the best experimental CECs ranging between 75% and 94% of the theoretical CEC with NH4+ as the replacement cation and 79% and 88% of the theoretical CEC with Cs+ as the replacement cation. The exchange efficiency was also measured as a function of ammonium concentration in the replacement solution (0.50, 1.00, 2.00 and 3.00 M). Experimental CECs ranged between 94% (0.5 M NH4Cl solution) and 99% (1 M NH4Cl solution) of the theoretical CEC for one epiclastic rock sample and between 79% (3 M NH4Cl solution) and 87% (2 M NH4Cl solution) of the theoretical CEC for one pyroclastic rock sample.

Sedimentary zeolite occurrences are widespread in Central and Western Anatolia, Turkey. Erionite occurrences in Central Anatolia have significant health implications for inhabitants of the region. The widespread occurrences of zeolites are generally associated with volcano-sedimentary rocks and consist of low-temperature forms. The aim of the work was to define specifically the formation mechanism and chemical characteristics of these volcano-sedimentary deposits, and particularly, the stability conditions for erionite. The first step was to construct chemical potential diagrams and calculate thermodynamic data for erionite and Ca-saponite. Then, equilibrium activity diagrams were calculated for the zeolites and related minerals in the system of Ca-Na-K-Mg-Fe-Al-Si and H2O. Stability diagrams for log [aCa2+/(aH+)2] — log [aNa+/aH+] and log [aCa2+/(aH+)2] — log [aK+/aH+] for various saturation phase activities of Al3+ and SiO2 (aq) were plotted for sedimentary conditions. The coexisting phases and chemical characteristics of the each deposit were evaluated by examination of the activity diagrams. Deposits which do not include some of the common sedimentary zeolites, possibly have high Al3+ activity (equal to or greater than gibbsite saturation) or low SiO(aq) activity (less than quartz saturation) during formation. In addition, erionite was found to be very sensitive to the alkalinity of the system and is stable in only a limited range of thermochemical conditions.