Mineralogical and thermal characteristics of synthetic Al-, Cr-, Mn-, Ni- and Ti-bearing goethites, synthesized via alkaline hydrolysis of metal-ferrihydrite gels, were investigated by powder X-ray diffraction and differential thermal analysis. Shifts in unit-cell dimensions were consistent with size of substituent metal ions and confirmed the incorporation of Al3+, Cr3+, Mn3+, Ni2+ and Ti4+ in the goethite structure. A weight loss of 6.2 wt.% for goethite containing 12.2 mol.% Ti, being significantly less than for stoichiometric goethite, is consistent with the replacement of Fe by Ti in the goethite structure coupled with the substitution of O2− ions for OH− (i.e. proton loss). These data provide the first confirmation of the direct replacement of Fe by Ti within goethite. Formation of multiple dehydroxylation endotherms for goethite containing 4.5 mol.% Al, 15.3 mol.% Mn and 12.2 mol.% Ti was not attributed to the decomposition of surface OH groups or related simply to the crystallinity of precursor goethite (‘high-a’ vs. ‘low-a’) as defined by the magnitude of a. Instead, endotherm doublet formation was associated with weight loss due to the dehydroxylation of goethite remaining after initial phase transformation to protohematite and to the evolution of OH− associated with the rapid increase in crystallite size of protohematite directed primarily along the a direction. Development of the first endotherm is due to initial dehydroxylation and transformation to protohematite. With continued heating of well ordered goethite or goethite containing moderate to high levels of substituent cations, domain growth along the a direction is delayed or inhibited to a critical point that provides enough thermal energy to enable goethite transformation to proceed to completion and for proto-hematite domain growth to occur. This results in the formation of a second endotherm. For less well ordered goethite and/or goethite containing only low levels of foreign metal cations, protohematite domain growth is not inhibited and proceeds continuously with heating to give only a single endotherm.

A series of organoclays with monolayers, bilayers, pseudotrilayers, paraffin monolayers and paraffin bilayers were prepared from montmorillonite by ion exchange with hexadecyltrimethylammonium bromide (HDTMAB). The HDTMAB concentrations used for preparing the organoclays were 0.5, 0.7, 1.0, 1.5, 2.0 and 2.5 times the montmorillonite cation exchange capacity (CEC). The microstructural parameters, including the BET-N2 surface area, pore volume, pore size, and surfactant loading and distribution, were determined by X-ray diffraction, N2 adsorption-desorption and high-resolution thermogravimetric analysis (HRTG). The BET-N2 surface area decreased from 55 to 1 m2/g and the pore volume decreased from 0.11 to 0.01 cm3/g as surfactant loading was increased from Na-Mt to 2.5CEC-Mt. The average pore diameter increased from 6.8 to 16.3 nm as surfactant loading was increased. After modifying montmorillonite with HDTMAB, two basic organoclay models were proposed on the basis of HRTG results: (1) the surfactant mainly occupied the clay interlayer space (0.5CEC-Mt, 0.7CEC-Mt, 1.0CEC-Mt); and (2) both the clay interlayer space and external surface (1.5CEC-Mt, 2.0CEC-Mt, 2.5CEC-Mt) were modified by surfactant. In model 1, the sorption mechanism of p-nitrophenol to the organoclay at a relatively low concentration involved both surface adsorption and partitioning, whereas, in model 2 it mainly involved only partitioning. This study demonstrates that the distribution of adsorbed surfactant and the arrangement of adsorbed HDTMA+ within the clay interlayer space control the efficiency and mechanism of sorption by the organoclay rather than BET-N2 surface area, pore volume, and pore diameter.

Palygorskite fibers growing along fault planes in the outcrops of a large fault zone in SE Spain (Carboneras Fault Zone: CFZ; Serrata de Níjar) were studied by X-ray diffraction, scanning electron microscopy-energy dispersive X-ray analysis, and transmission electron microscopy-analytical electron microscopy. The structural formulae, calculated per half unit-cell, is: Si7.95Al0.05O20(Al1.93Fe0.08Mg1.92) (OH)2(OH2)4Na0.09K0.01Ca0.034(H2O). The samples have minor tetrahedral substitutions, with Mg/Al ratios close to one, and contain very small amounts of Fe3+. The number of octahedral cations per half unit-cell is 3.93. The fault-hosted palygorskite shows macroscopic ductile features including incipient foliation. Based on field and laboratory observations, as well as on regional geological evidence indicating the existence of widespread hydrothermal processes along the Serrata de Níjar and surrounding areas, we suggest that palygorskite may have formed during ongoing deformation in the CFZ, as a precipitate from Mg-rich hydrothermal fluids.

The strong adsorption to kaolinite of four polyaromatic, cationic dyes (9-aminoacridine, 3,6-diaminoacridine, azure A and safranin O), which adsorb much less to alumina or silica, was investigated by means of acid-base titrations, measurements of adsorption at varying pH and dye concentration, and by ATR-FTIR spectroscopy. The four dyes adsorb to kaolinite to similar extents, with little change over the pH range 3–10, but at higher pH (above the pKas of the dyes) the adsorption of 9-aminoacridine and 3,6-diaminoacridine decreases, that of azure A increases, and that of safranin O stays approximately constant. Although the dyes adsorb to kaolinite much more strongly than metal ions do, titration and spectroscopic data show that there is only limited chemical interaction between the adsorbed dyes and the kaolinite surface. The results indicate that electrostatic interaction between the dye molecules and the kaolinite surface is necessary for adsorption, but that hydrophobic interactions also contribute. It is proposed that the relatively hydrophobic silica faces of kaolinite, which carry low-density permanent negative charge, facilitate aggregation and adsorption of the positively charged, flat, aromatic dye molecules.

The competitive adsorption to kaolinite between Cd(II) and four polyaromatic dyes (9-aminoacridine, 3,6-diaminoacridine, azure A and safranin O) was studied in 5 mM KNO3 at 25°C. Under these conditions, Cd adsorbs to the silica face of kaolinite between about pH 4 and 6.5, but at higher pH, adsorbed Cd is progressively relocated to the crystal edges. In the presence of dye, less Cd adsorbed to kaolinite below pH 7. If sufficient dye was added to saturate the kaolinite surface, Cd adsorption was totally suppressed up to ∼pH 6. At higher pH, Cd followed the characteristic pattern for edge adsorption. In separate experiments 9-aminoacridine and azure A displaced pre-adsorbed Cd from kaolinite. The displacement curves were initially linear, with one Cd ion being displaced for every 13 dye molecules adsorbed at pH 5.5, and one Cd ion for every 35 dye molecules at pH 7.5. The interpretation of these results is that the dyes bind to kaolinite much more strongly than Cd(II) does, but only to the silica face.

The zeolites and coexisting minerals of the silicic vitric tuffs in the Alaçatı (Çeşme) area, west of İzmir (Turkey), were studied. Mordenite is the most abundant zeolite in tuffs of the Alaçatı area and usually coexists with clinoptilolite-heulandite, smectite and calcite. Opal-CT was identified by means of its crystal morphology and EDX spectrum. Scanning electron microscopy (SEM) revealed the relative age relationships between the zeolites and coexisting minerals, namely mordenite, clinoptilolite-heulandite, smectite, calcite, and, in addition, opal-CT. Smectite consistently crystallized earlier than any of the zeolites, and it occasionally coats the outer walls of some of the vitric material. The zeolites are commonly located on the smectite, although some mordenites were observed to be in direct contact with glass shards that lacked a smectite coating. Clinoptilolite-heulandite formed after smectite and before mordenite. Opal-CT is seen to postdate both smectite and needle-shaped mordenite. Calcite was probably the latest mineral to crystallize in the Alaçatı tuffs. The zeolites in the tuffs of the Alaçatı area formed by dissolution of silicic vitric tuffs by Na- and Ca-rich thermal waters which passed through the fracture zone. The appearance of zeolites together with smectite along this zone may be attributed to a semi-open system which subdivided into smaller closed systems. Small changes in the pH and chemical composition of the thermal waters during alteration produced the corrosion effects observed by SEM. Small amounts of clinoptilolite-heulandite were corroded prior to crystallization of coexisting mordenite. The different compositions of the thermal waters were probably inherited from water that resulted from mixing of thermal and groundwaters.

The objective of this study was to determine whether smectites abiotically catalyze transformation of glucose under conditions relevant to soil organic matter (SOM) formation. Four smectites saturated with Na, Ca, Fe and Al were incubated under abiotic conditions with glucose solutions for 21 days at 37°C. After the incubations, soluble organic C recoveries ranged from 95 to 109.3%, relative to the amount of C added as glucose; however, glucose recoveries in the solutions ranged from 18.3 to 98.3%. The results indicate that a significant amount of the added glucose was abiotically transformed to soluble organic compounds other than glucose during the incubations. In general, glucose recoveries decreased with the acidic character of smectites: SWa-1 > Panther > Otay. Also, within clays, glucose recoveries decreased as the exchangeable cation became more acidic: Na > Ca > Al. Higher glucose recoveries were obtained for ‘Fe-rich’ smectites relative to ‘Fe-poor’ smectites, suggesting that Fe-oxyhydroxy coatings on smectite surfaces inhibit the transformation of glucose. High-pressure liquid chromatography analysis of the incubation solutions revealed small peaks for 5-(hydroxymethyl)-2-furaldehyde along with peaks for other unknown compounds. The results suggest that under conditions similar to those found in soils, smectites catalyze glucose dehydration to form furfural compounds. Polymerization of furfural compounds may be a major pathway leading to the formation of new humic materials in soils.

Talc deposits, located mainly in three areas of north-central Turkey, are present in the ophiolitic series of the Cretaceous and in siliciclastic rocks of the Paleocene. Talc deposits related to ophiolites are between tectonite and cumulate occurring as beds and/or lenses and 0.1–3 cm thick fracture fillings within a 5 m brecciated zone with a vein-type bedding. Sedimentary-hosted talc beds and semi-rounded to angular talc grains (0.1–2 cm) range in thickness from 0.1 to 30 cm within marls and conglomerates. Talc veins form lenses (a few meters long) and spheroidal and/or ellipsoidal nodules (1–10 cm). Calcite, dolomite, serpentine and/or mixed-layered illite-smectite (I-S) minerals are encountered in the talc samples. Serpentine with positive U and Hf anomalies, and talc with positive Nb and Zr anomalies, and negative Ta and Ce anomalies are typically depleted in P and Ti, based on chondrite-normalized trace element patterns. The light rare earth element content of sedimentary-hosted talc with a negative Gd anomaly is richer than those of ultramafic-hosted talc with a negative anomaly for Eu as well as serpentine. Significantly, talc with a uniquely sedimentary origin tends to be the principal source of Nb, Hf, Zr, La, Ce, Pr and Nd with respect to serpentine. δ18O and δD values for talc range from +13.8 to +17.5‰ and −60 to −36‰, and those of serpentine are +9.4 and −88‰, indicating supergene conditions for sedimentary-hosted talc and hypogene for ultramafic-hosted talc. When compared with seawater, δ18O data indicate temperatures of 68°C and 80–98°C for the sedimentary- and ultramafic-hosted talc formations, respectively, and 100°C for serpentine, suggesting that talcification and serpentinization of ultramafic rocks both occurred at nearly the same time with various stages. All data show that the talc occurrences are divided into two types based on their mode of formation. The first corresponds to a serpentinization stage within the ophiolites. The others are the neoformation products of sedimentary deposition, diagenetic and post-diagenetic processes, respectively. Sedimentary-hosted talc also seems to have inherited trace element and isotopic compositions from the parent ultramafic rocks.

The reduction of structural Fe in smectite is mediated either abiotically, by reaction with dithionite, or biotically, by Fe-reducing bacteria. The effects of abiotic reduction on clay-surface chemistry are much better known than the effects of biotic reduction. Since bacteria are probably the principal agent for mediating redox processes in natural soils and sediments, further study is needed to ascertain the differences between biotic and abiotic reduction processes. The purpose of the present study was to compare the effects of dithionite (abiotic) and bacteria (biotic) reduction of structural Fe in smectites on the clay structure as observed by infrared spectroscopy. Three reference smectites, namely, Garfield nontronite, ferruginous smectite (SWa-1), and Upton, Wyoming, montmorillonite, were reduced to similar levels by either Shewanella oneidensis or by pH-buffered sodium dithionite. Each sample was then analyzed by Fourier transform infrared spectroscopy (FTIR). Parallel samples were reoxidized by bubbling O2 gas through the reduced suspension at room temperature prior to FTIR analysis. Redox states were quantified by chemical analysis, using 1, 10-phenanthroline. The reduction level achieved by dithionite was controlled to approximate that of the bacterial reduction treatment so that valid comparisons could be made between the two treatments. Bacterial reduction was achieved by incubating the Na-saturated smectites with S. oneidensis strain MR-1 in a minimal medium including 20 mM lactate. After redox treatment, the clay was washed four times with deoxygenated 5 mM NaCl. The sample was then prepared either as a self-supporting film for OH-stretching and deformation bands or as a deposit on ZnSe windows for Si-O stretching bands and placed inside a controlled atmosphere cell also fitted with ZnSe windows. The spectra from bacteria-treated samples were compared with dithionite-treated samples having a similar Fe(II) content. The changes observed in all three spectral regions (OH stretching, M2-O-H deformation, and Si-O stretching) for bacteria-reduced smectite were similar to results obtained at a comparable level of reduction by dithionite. In general, the shift of the structural OH vibration and the Si-O vibration, and the loss of intensity of OH groups, indicate that the bonding and/or symmetry properties in the octahedral and tetrahedral sheets changes as Fe(III) reduces to Fe(II). Upon reoxidation, peak positions and intensities of the reduced smectites were largely restored to the unaltered condition with some minor exceptions. These observations are interpreted to mean that bacterial reduction of Fe modifies the crystal structures of Fe-bearing smectites, but the overall effects are modest and of about the same extent as dithionite at similar levels of reduction. No extensive changes in clay structure were observed under conditions present in our model system.

Bentonite from the ‘Bogovina’ coal mine in Serbia, was characterized. The influence of acid treatment on its composition, as well as mathematical descriptions of this influence are reported. The purpose of this work was to correlate the concentration of the acid used for the treatment with the resulting bentonite composition. X-ray diffraction (XRD), infrared spectroscopy and quantitative chemical analysis were employed to define the changes caused by acid treatment.

The contents of all the cations, except Si, decreased exponentially with increasing concentration of the HCl used for the treatment of the bentonite. This approach was tested on previously published data and was shown to be valid.

The basal reflections of smectite decreased gradually and eventually disappeared after intense treatment, while the other reflections remained in the XRD patterns of all the samples, but decreased slightly with increasing acid strength. In addition, the amount of X-ray amorphous matter formed increased rapidly with increasing acid concentration up to 4.5 M. With further increase in the acid strength, the amount of X-ray amorphous matter remained virtually constant.

The early stages of amphibole weathering result in the crystallization of several clay mineral species: tri- and dioctahedral smectites, interstratified dioctahedral kaolinite-smectite (K-S), and halloysite. Each clay mineral crystallizes into specific microsites which develop from etch pits along specific crystallographic directions in the host amphibole. Two types of microsites are recognized according to their location in the amphibole crystal and their clay mineral crystallizations. The first type is a plane surface related to the (110) amphibole cleavages where saponite particles crystallize in a characteristic honeycomb texture. The second type is a ‘sawtooth’ (001) fracture surface generated by etch-pit coalescence where (1) platy K-S particles crystallize directly in contact with the amphibole at the top of ‘teeth’, (2) halloysite particles with tubular habits crystallize directly in contact with the amphibole on the side of the ‘teeth’, and/or on the K-S particles, and (3) montmorillonite crystallizes in the central part of the (001) fracture as a layer with honeycomb texture in contact with the K-S platelets located at the top of ‘teeth’. The microtextural relationships between the clay minerals and their host mineral suggest the following crystallization sequence: (1) saponite and montmorillonite crystallize first on the (110) and (001) surfaces, respectively; (2) as amphibole dissolution proceeds perpendicular to the (001) fracture planes, montmorillonites continue to form in the middle part of the widening fracture whereas K-S crystallizes on the ‘sawtooth’ termination; (3) in the last stage of weathering, tubular halloysite crystallizes on the side of the ‘teeth’, and/or on the K-S.

Many soils in southern Switzerland have a black color, contain a large amount of soil organic matter (SOM) and seem to have some andic properties although they did not develop on volcanic parent material. We investigated three typical ‘black’ soils to determine the mechanisms of (clay) mineral formation and transformation. We measured total element pools as well as the dithionite-, pyrophosphate-and oxalate-extractable fractions (Fe, Al, Si). The clay fraction (<2 µm) was analyzed using X-ray diffraction and FTIR spectroscopy. Iron speciation in the solid phase was determined by Mössbauer spectroscopy. With increasing weathering conditions, the plagioclase (albite) content decreases, trioctahedral species in the clay fraction such as biotite, chlorite or trioctahedral vermiculite either decompose or transform into a dioctahedral mineral such as dioctahedral vermiculite or hydroxy interlayered smectite (HIS). Typical weathering products were hydroxy interlayered vermiculite (HIV), HIS, interstratified minerals and kaolinite. The oxidation of Fe(II) into Fe(III) was evident and contributes to the transformation of trioctahedral mineral species into dioctahedral ones. In one soil, a large part of the Fe (up to 41%) was found in the form of Fe oxides. In the surface horizon, the poorly crystalline mineral ferrihydrite was dominant, while in the subsoil goethite prevailed. Maghemite (or maghemite/hematite mixture) was, furthermore, found in distinct concentrations down to a depth of ∼50 cm. The formation of this mineral requires high temperatures which means that a forest fire can influence soil mineralogy down to a considerable depth. The specific climatic conditions with periods of strong humidity alternating with periods of winter droughts, sporadic fire events and the relatively large content of poorly crystalline fractions of Fe and Al contributed to the stabilization of SOM.

Simple extended constant capacitance surface complexation models have been developed to represent the adsorption of polyaromatic dyes (9-aminoacridine, 3,6-diaminoacridine, azure A and safranin O) to kaolinite, and the competitive adsorption of the dyes with Cd. The formulation of the models was based on data from recent publications, including quantitative adsorption measurements over a range of conditions (varying pH and concentration), acid-base titrations and attenuated total reflectance-Fourier transform infrared spectroscopic data. In the models the dye molecules adsorb as aggregates of three or four, forming outer-sphere complexes with sites on the silica face of kaolinite. Both electrostatic and hydrophobic interactions are implicated in the adsorption processes. Despite their simplicity, the models fit a wide range of experimental data, thereby supporting the underlying hypothesis that the flat, hydrophobic, but slightly charged silica faces of kaolinite facilitate the aggregation and adsorption of the flat, aromatic, cationic dye molecules.

The aim of this work was to investigate whether neoformed Ni-phyllosilicates can be observed and identified using transmission electron microscopy (TEM) in combination with energy dispersive spectroscopy (EDS). The investigations focused on Ni-phyllosilicates formed from Ni-doped montmorillonite. The reaction conditions (pH 8, [Ni]initial = 660 and 3300 µM, 0.2 M Ca(NO3)2) employed were similar to those used in previous polarized extended X-ray absorption fine structure (P-EXAFS) investigations of neoformed Ni-phyllosilicates in a Ni-montmorillonite system.

The TEM investigations of Ni-doped montmorillonite revealed the presence of small, thin particles consisting of coherent stacks that yielded only three to five lattice fringes with spacings consistent with smectites. These small particles were neoformed phyllosilicates, based on the fact that the small particles were only observed in Ni-doped samples and their Ni content, as determined from EDS analysis, was high (up to 10 wt.% NiO). Furthermore, the particles did not possess the characteristic properties of montmorillonite particles, such as a 2:1 Si to Al ratio; instead these particles were rich in Si (up to 75 wt.% SiO2). Unlike montmorillonite, these particles did not contain any Fe. The particles were also significantly more resistant to electron beam damage than montmorillonite particles, and EXAFS measurements confirmed the presence of neoformed Ni-phyllosilicates.

The TEM study further indicates the presence of a variety of additional minerals (e.g. cristobalite, halloysite) and an X-ray amorphous Si-rich phase. A Ni signal could only be detected in the latter phase at high Ni loadings (403 µmol/g), suggesting that Ni uptake at low metal loadings (<90 µmol/g) is mainly controlled by the neoformation of phyllosilicates.

The dissolution of brucke, Mg(OH)2, on the (001) surface was investigated using in situ atomic force microscopy in solutions at near-neutral pH. Dissolution proceeded by the formation of crystallographically oriented triangular etch pits with monolayer step and expansion of the pits. The sides of the triangle are parallel to the [100], [110] and [010] directions of the brucite structure, and the orientation of lines from the center of the triangle to the three apices are along the [210], $[\overline{1}10]$$[\bar 110]$ and $[\overline{1}\overline{2}0]$$[\bar 1\bar 20]$ directions. This orientation may produce pit edges where OH groups coordinate to two Mg2+. Although triangular etch pits with monolayer depth formed mostly at random on the (001) surface, concentric pits penetrating several layers were also observed. Etch pits with spiral steps were rarely observed. Coalescence of the pits resulted in stranded terraces that diminished in size rapidly and formed a rounded irregular form. The step-retreat velocity around the triangular pit is 0.015–0.04 nm/s at pH 5–8. The retreat velocity around the stranded terraces was about three times more rapid than that around the triangular etch pits.

Various secondary phases formed during alteration/dissolution of HLW (high-level nuclear waste) borosilicate glass represent a significant retention potential for radionuclides including divalent actinides. The trioctahedral smectite, hectorite, Na0.7[Li0.7Mg5.3Si8O20(OH)4], is one of the secondary phases identified within the alteration layer of corroded HLW glass. Numerous studies have clearly shown that many radionuclides are associated with clay minerals and the migration of radionuclides is strongly reduced by complexation. Due to the structural complexity and chemical variability of smectites, sorption of radionuclides involves several sorption mechanisms: (1) adsorption via inner-sphere and outer-sphere complexation; (2) cation exchange in the interlayer; and (3) incorporation into the smectite structure. Up to now, it was not known whether trivalent actinides such as Cm(III) and Am(III) become incorporated into the crystal structure of clay minerals like hectorite. We have used a new method, developed by Carrado et al. (1997b), to synthesize a Eu- and a Cm-containing hectorite, utilizing Cm(III) and chemically homologous Eu(III) coprecipitated with Mg(OH)2 as a precursor. X-ray diffraction, Fourier transform infrared spectroscopy and atomic force microscopy identified the reaction products unambiguously as hectorite. The sorption mechanisms of Eu associated with the synthesized hectorite were investigated by time-resolved laser fluorescence spectroscopy (TRLFS). An unhydrated Eu species (fluorescence lifetime 930 µs) and a partly hydrated Eu species (fluorescence lifetime 381 µs) could be identified. The unhydrated Eu species can be interpreted as incorporating Eu(III) into the hectorite structure or a remaining X-ray amorphous silica phase. The spectra of Eu hectorite and the Eu silica complexation are too similar to permit differentiation between these species, but dialysis experiments demonstrated the close association of the unhydrated Eu species with the crystalline hectorite phase. Time-resolved laser fluorescence spectroscopy (TRLFS) measurements identified the same incorporated Eu species as long as the Eu hectorite was stable under acidic conditions. The stability of the Eu hectorite could be shown by the dialysis experiment over a time period of 160 h. Between 160 und 500 h, hectorite became unstable and a new silica phase was detected. In addition, TRLFS measurements of the Cm-containing hectorite confirmed the incorporation of actinides in the smectite structure. The Cm-hectorite and Cm-silica species can be differentiated unambiguously by TRLFS. In order to differentiate between coprecipitated and surface-sorbed Eu species, batch sorption studies were performed with synthetic Eu-free hectorite. For the surface-sorbed Eu species, a fluorescence lifetime of 284 µs (3.1 H2O molecules) was found, which clearly differs from the coprecipitated species with a fluorescence lifetime of 930 µs. The different lifetimes indicate a different chemical environment. Based on all observations it seems to be very likely that trace amounts of Cm/Eu occupy a distorted octahedral site in the hectorite.

Compacted Na-bentonite clay barriers, widely used in the isolation of solid-waste landfills and other contaminated sites, have been proposed for a similar use in the disposal of high-level radioactive waste. Molecular diffusion through the pore space in these barriers plays a key role in their performance, thus motivating recent measurements of the apparent diffusion coefficient tensor of water tracers in compacted, water-saturated Na-bentonites. In the present study, we introduce a conceptual model in which the pore space of water-saturated bentonite is divided into ‘macropore’ and ‘interlayer nanopore’ compartments. With this model we determine quantitatively the relative contributions of pore-network geometry (expressed as a geometric factor) and of the diffusive behavior of water molecules near montmorillonite basal surfaces (expressed as a constrictivity factor) to the apparent diffusion coefficient tensor. Our model predicts, in agreement with experiment, that the mean principal value of the apparent diffusion coefficient tensor follows a single relationship when plotted against the partial montmorillonite dry density (mass of montmorillonite per combined volume of montmorillonite and pore space). Using a single fitted parameter, the mean principal geometric factor, our model successfully describes this relationship for a broad range of bentonite-water systems, from dilute gel to highly-compacted bentonite with 80% of its pore water in interlayer nanopores.

Bentonite, biotite, illite, kaolin, muscovite, vermiculite and zeolite were acidified or alkalized with HCl orNaOH of concentrations 0.0, 0.1, 1.0 and 5.0 mole dm−3 at room temperature for 2 weeks and converted into Ca homoionic forms. Low-temperature nitrogen and room-temperature water-vapor adsorption-desorption isotherms were used to characterize the mineral pores of radii between 1 and 30 nm. Nanopore volumes, size distributions, average radii and fractal dimensions were calculated. Values calculated from the nitrogen isotherms differed from those derived from water-vapor data. With an increase of the acid-treatment concentration, the pore volumes measured using both adsorption techniques increased markedly for all minerals. The pore radii measured from nitrogen isotherms appeared to decrease for all minerals except zeolite, while the pore radius calculated from water-vapor data increased in most cases. The fractal dimension measured from water vapor isotherms decreased in all cases indicating smoothing of the mineral surfaces and decrease in pore complexity. No well defined trends in any of the pore parameters listed above were noted under alkaline treatment. In the reaction of each mineral with acid and alkali treatments, the individual character of the mineral and the presence of impurities seems important.

Alumina-pillared montmorillonite clays (Al-PILC), prepared under ultrasonic (US) agitation and normal stirring (S) methods, have been used as a host material to encapsulate Co phthalocyanine (CoPc) complex. The amount of Co varies from 0.27 to 1.48 wt.% in the samples, depending on the input concentration of Co. Powder X-ray diffraction and other characterization techniques reveal that the structure of Al-PILC remains intact after the incorporation of the complex into the pores through a pyridine solution of the complex by ultrasonic agitation. A substantial decrease in the BET surface area and total pore volume of Al-PILC points to the occupation of the CoPc moieties within the porous structure of the pillared clay. This is further supported by the observation of a band at 1489 cm−1 in the Fourier transform infrared (FTIR) spectra of the encapsulated samples. The FTIR and diffuse reflectance ultraviolet-visible (DRUV-Vis) spectral results indicate that the encapsulated CoPc complex in the clay matrix undergoes distortion in order to accommodate itself within the pores of the Al-PILC. The encapsulated samples prepared by ultrasonification show better dispersion of the complex than the samples prepared under normal stirring conditions. Compared to the ‘neat’ complex, the encapsulated samples (CoPc in Al-PILC) exhibit greater turnover in the test reaction of the oxidation of benzyl alcohol to benzaldehyde with tertbutyl hydroperoxide as the oxidant at 373 K. The method of preparation and consequent site isolation of CoPc in Al-PILC influence the catalytic activity.

Todorokite is a common Mn oxide (with a tunnel structure) in the Earth surface environment, and can be obtained by hydrothermal treatment or refluxing process from precursor buserite with a layered structure. Several chemical reaction conditions for the phase transformation from Na-buserite to todorokite at atmospheric pressure were investigated, including temperature, pH, crystallinity of precursor Na-buserite, the amount of the interlayer Mg2+ of the Mg-buserite and clay minerals. The results showed that the conversion rate and crystallinity of todorokite decreased with falling temperature, and Mg-buserite could not be completely transformed to todorokite at lower temperatures (40°C). The poorly crystalline Na-buserite could be converted into todorokite more easily than highly crystalline Na-buserite. Todorokite can be prepared at pH 5–9, but the rate of conversion and crystallinity of todorokite did vary with pH in the order: neutral ≈ alkali > acidic. The conversion rate of todorokite decreased with decreasing interlayer Mg2+ content of the Mg-buserite. The presence of montmorillonite or goethite slowed the formation reaction of todorokite in the refluxing process, and the reaction time was prolonged when the amounts of those minerals were increased.