Acid and non-acid forms of kaolinite clays were found by potentiometric and conductometric titrations to possess a weak acid species, the concentration of which was increased by acidic preparation conditions and by the presence of soil organic matter bound to the clay. A stronger acid species was also found in untreated and in organic-free, HCl-treated samples (washed free of excess acid). The end points for organic-free and/or ion-exchanged samples were used to predict the end points for untreated samples. A surface-chemical model involving MOH2+, MOH, and MO− species (where M = Al and/or Fe) was fitted to the titration data and to the cation-exchange capacities. MOH2+ is the stronger acid and MOH the weaker acid; exchange of Na+ counterions by H+ converts MO−Na+ sites to MOH sites. Humic acid was probably complexed or chelated to some hydroxylated Al/Fe sites through COOH and phenolic OH groups. The COOH groups contributed supplementary stronger acid species which were not exchangeable, whereas the OH groups contributed supplementary weaker acid species and also increased the CEC relative to that for organic-free samples.

The conductivites of the Na and H ion-exchanged forms of kaolinitic clay rejects from sand-washing operations, both purified and as found naturally as a complex with soil organic matter, were examined. The two Na-clays showed linear conductivity-concentration characteristics, each having two regions with different slopes intersecting at ∼3.3% by weight of clay, which probably reflect a structural change from sol to gel. In the gel region, only the Na-counterions conducted, the reduction in conductivity with concentration being due to a smaller proportion of these ions in the Gouy layer and/or a decrease in their mobilities. In the sol, an additional, concentration-dependent conductivity arose from the electrophoretic motion of clusters of clay particles which gradually broke down on dilution. The two acid clays showed curved conductivity-concentration characteristics consistent with a weak acid dissociation equilibrium; the pKa values of 6.37 to 6.56 are close to those determined independently from titration with alkali. A stronger acid species detected in the titrations was not seen in the conductivity. The MOH2+/MOH/MO− model of the clay-surface species and one set of the predicted concentrations of each species (see preceding paper) are consistent with the observed conductivities. The MOH2+ species probably bridged the edges and faces of clay particles so that the H atoms were identical, but became different when alkali was added.

The most common means of reducing the particle size of solids is by grinding, a process which can affect the surface properties and the behavior of the solid in later stages (granulation, compaction, etc.), and which can influence the end-use properties of the final product. Inverse gas chromatography (IGC) measurements were used here to evaluate the influence of grinding, in a ball mill, on attapulgite. The milling experiments were performed in dry media for various periods. After 30 min of grinding, significant decreases in the particle size and specific surface areas were observed when calculated using different probes. No noticeable variation in the surface properties was observed by IGC either at infinite dilution or at finite concentration, however. In particular, the distribution functions of the adsorption energies (DFAE), giving information about the surface heterogeneity for both an apolar probe (octane) and a polar probe (isopropanol), remained unchanged, regardless of the grinding time. The stability of the surface energy with respect to the grinding process was seen to be related to the particular fibrous structure of the attapulgite clay.

The contamination of aquatic environments by toxic metals such as radionuclides is of great concern because of the tendency of those metals to accumulate in the vital organs of humans and animals, causing severe health problems. The objective of this study was to investigate the use of natural and modified magadiite clay as an adsorbent to remove Th(IV), U(VI), and Eu(III) from aqueous solutions. Magadiite from the Amazon region, Brazil, was modified chemically with 5-mercapto-1-methyltetrazole (MTTZ) using a multi-step or heterogeneous synthesis pathway. The natural and modified materials were characterized using 29Si and 13C nuclear magnetic resonance, scanning electron microscopy, nitrogen gas adsorption, and elemental analysis. The physical-chemical properties of the chemically modified magadiite sample were modified, e.g. the specific surface area changed from 35.0 to 678.9 m2 g−1. The ability of the magadiite to remove Th(IV), U(VI), and Eu(III) from aqueous solution was then tested by a series of adsorption isotherms adjusted to a Sips equation. The effects of properties such as pH, contact time, and metal concentration on the adsorption capacity were studied. The adsorption maxima were determined to be 7.5 × 10−3, 9.8 × 10−3, and 12.9 × 10−3 mmol g−1 for Th(IV), U(VI), and Eu(III), respectively. From calorimetric determinations, the quantitative thermal effects for all these cations/basic center interactions gave exothermic enthalpy, negative Gibbs free energy, and positive entropy, confirming the energetically favorable conditions of such interactions at the solid/liquid interface for all systems.

The influence of organics on the crystallization of Al precipitates has been well documented. However, the effects of organics and ageing on the transformation and structural configuration of Al precipitates in relation to their surface and charge properties are not fully understood. This study investigated the structural, microporous and surface properties of Al precipitates formed under the influence of tannate and ageing. The Al precipitates were synthesized at an initial Al concentration of 7 × 10−3 M, an OH/Al molar ratio (MR) of 3.0, and initial tannate/Al MRs of 0, 0.001, 0.01 and 0.1, and aged for 1, 10 and 40 days. As indicated by a decrease in gibbsite and bayerite and an increase in the oxalate-extractable Al contents, the non-crystalline precipitates increased with the increase of the initial tannate/Al MR. This observation is in accord with the X-ray diffraction and Fourier transform infrared (FTIR) data. The impact of tannic acid on the nature of the Al precipitates is also reflected in the increase of the contents of the pyrophosphate-extractable Al, which is indicative of organically bound Al. This observation is in agreement with the increase in the intensity of characteristic FTIR absorption bands of tannate and the organic C and adsorbed water contents. The decrease in the crystallinity of Al precipitates with increase in the tannate/Al MR resulted in the development of microporosity, increase in BET specific surface area and decrease of the average pore diameter and point of zero salt effect (PZSE). The FTIR absorption bands characteristic of tannate of the Al precipitates became weaker with ageing, in accord with the ageing-induced decrease in the contents of organic C and pyrophosphate-extractable Al. Ageing drastically decreased the BET specific surface area of the Al precipitates formed in the absence of tannate but this effect was less conspicuous for the products formed at the tannate/Al molar ratio of 0.1. The ageing-induced change in the PZSE of the Al precipitates formed both in the absence and presence of tannate was not significant. The results accomplished in this study are of fundamental significance to our understanding of the combined effects of organics and ageing on structural configuration of hydrolytic precipitates of Al in relation to their microporosity, surface and charge properties in the environment.

The preparation of porous materials from clay minerals by selective leaching is of interest because it yields residues with large specific surface areas that can be used as adsorbents of contaminants or as catalysts. Grinding produces surface modifications and therefore may significantly influence the leaching behavior. The aim of this paper is to study the effect of grinding and leaching on the structure of the vermiculite from Santa Olalla, Spain, using 57Fe Mössbauer spectroscopy, X-ray diffraction, infrared spectroscopy, and specific surface area (SBET) measurements. The study shows that grinding destroys the long range order of the vermiculite, but leaves the local structure in the environment of the Fe atoms intact, at least up to a grinding time of 10 min. The Mössbauer study shows that there is no Fe3+ in the tetrahedral sheets and that grinding does not lead to a significant oxidation of the structural Fe. Vermiculite ground for 4 min and leached with 1 M HCl solution at 80°C over a 24 h period was decomposed to X-ray amorphous silica with a very large specific surface area (SBET = 720 m2g−1) and with total pore volume of 0.586 cm3 g−1, whereas an unground sample leached with the same acid concentration yielded a specific surface area of only 504 m2 g−1. Most of the Mg2+ and Al3+ are removed from the ground sample after leaching with 1 M HCl, while large percentages of Fe2O3 remain with the X-ray amorphous silica. In unground vermiculite leached with 1 M HCl, a considerable amount of vermiculite remains in the residue. A sample ground for 4 min and treated with 0.25 M HCl also shows the typical vermiculite Mössbauer spectrum with an Fe2+/Fe3+ ratio similar to that of the unground vermiculite. The samples ground for 2 or 4 min and treated with 1 M HCl solution have an orange color and, according to the Mössbauer spectra, only Fe3+ remains. Mössbauer spectra of these samples taken at 4.2 K reveal the presence of akaganéite.

Non-ionic surfactants Brij 56 and Igepal CO 720, containing hydrophilic poly(ethylene oxide) (PEO) segments, expanded smectite from 1.5 nm to 1.7 nm at room temperature. The surfactant-smectite composites had larger layer spacings than Ca-smectite after heat treatment. The surfactant-smectite composites were solvated and expanded to 1.8–1.9 nm by polar solvents, glycerol and water, but were not affected by the non-polar or weakly polar solvents, toluene, hexane or octanol. The hydrophilic PEO segments of non-ionic surfactants would logically access the interlayer spaces of smectite whereas the hydrophobic segments extend away from the mineral. The molecular structure and solvation properties suggest that the surfactant molecules are probably concentrated in the margin area of the interlayer galleries forming an annular ring structure between two neighboring silicate sheets. Only two layers or less of the surfactants could access the interlayer galleries of smectite and layer spacings did not exceed 1.8 nm even where excess surfactant was introduced into the composites. The layer spacings of the surfactant-smectite composites were well preserved during water or electrolyte solution washings, indicating stability of most non-ionic surfactant molecules in the interlayer galleries even though ∼30% of the adsorbed Igepal CO 720 was desorbed by exhaustive washing. The non-ionic surfactant treatment preserved >80% of the CEC of the smectite. The interlayer cations of the resulting surfactant-smectite were exchangeable as in the untreated smectite. Therefore, the non-ionic surfactant-smectite was much more efficient at removing heavy metal ions than activated carbon or cationic surfactant-treated smectite. The surfactant-smectite composites effectively removed aromatic chlorophenols from a pH 4.9 acetate buffer solution while untreated smectite did not adsorb these molecules. The enhanced adsorption of the aromatic compounds is attributed to the aliphatic segments of the two surfactants.

The iron chemistry of aluminosilicates can markedly affect their adsorption properties due to possible changes in surface charge upon exposure to a variety of processes in the environment. One of these processes is chemical leaching, but to date little has been reported on the susceptibility of structural Fe to chemical leaching. The purpose of the current study was to determine the effects of solution pH on the stability of structural Fe in kaolinites, illite, and bentonite and the potential for formation of ancillary (oxyhydr)oxides. Structurally bound Fe does not participate in sorption properties but Fe that is released and phase transformed during leaching could take part in adsorption processes and form complexes and/or covalent bonds via Fe ions. Five different Fe-bearing clay minerals were treated in 0.5 M and 2 M HCl, distilled H2O, 0.1MKCl, and 0.5MKHCO3 for 24 h. The amount of Fe leached varied from 10 μg g-1 (for 0.1 M KCl) to 104 μg g-1 (for 2 M HCl) depending on the leaching agents. Acidic and water treatments indicated a relative independence of leached Fe on the initial Fe content in the clay and, conversely, a heavy dependence on the crystallinity of initial Fe phases. Well crystallized Fe(III) was stable during the leaching process, while poorly crystallized and amorphous Fe(III) phases were less stable, forming new ion-exchangeable Fe3+ particles. Under alkaline conditions, no relation between Fe crystallinity and mobility was found. The structural and surface changes resulting from leaching processes were identified by equilibrium adsorption isotherms. In kaolinite, the specific surface area (SBET) and porosity changed independently of Fe leaching due to the stability and crystallinity of Fe. In bentonite, the number of micropores was reduced by their partial saturation with Fe3+ particles caused by poorly crystallized and more reactive Fe forms during the leaching process. Potential phase transformations of Fe were characterized by the voltammetry of microparticles; well crystallized Fe(III) oxides remained stable under leaching conditions, while poorly crystallized and amorphous Fe(III) phases were partially dissolved and transformed to reactive Fe3+ forms.

Citrate is distributed widely in the Earth’s surface environments as a biological product released by microbes and plants. Citrate is also often used as a chelating agent for the selective dissolution of iron coatings and free iron oxides in soils. Adsorption experiments of Cs+ and IO3− before and after the complexation of citrate with the pseudoboehmite surface were conducted to evaluate the effects of citrate on the adsorption of these ions on the surface of pseudoboehmite. Additional adsorption experiments of Cs+ and IO3− after the decomposition of citrate adsorbed on the pseudoboehmite surface were also performed to confirm the recovery of the original surface properties. Citrate decomposition was carried out by means of 10% H2O2 treatments at 75°C and pH 5, 7, and 9. The results indicated that citrate complexation decreased remarkably the adsorption of both Cs+ and IO3− in the pH range 3–10, which was due to a decrease in the number of active charged sites available for adsorption of these ions. Decomposition of citrate adsorbed on the pseudoboehmite surface was found to be complete after three rounds of treatment with 10% H2O2 at 75°C and pH > 7. After the decomposition of citrate adsorbed on the pseudoboehmite surface, the adsorption of both Cs+ and IO3− was restored completely to the initial amounts before citrate complexation, and the inhibition effect of citrate on the adsorption of these ions disappeared under all pH conditions.

Saponitic bentonite mined in the Magan deposit (Toledo, Spain), has been classified as a suitable clay barrier in the storage of high-level radioactive waste. Several hydrothermal alteration assays have been carried out in Teflon reactors at 45, 60, 90, 120, 175 and 200°C for periods of up to 1 y. The mineral components of bentonite are stable below 175°C. At and above this temperature, the accessory sepiolite transforms into a monomineral phase of saponitic composition. The texture of the clay also changes. A rise in temperature above 120°C causes a decrease in the proportion of the <2 μm size-fraction, a reduction of BET and total surface areas and an increase in the relative volume of micropores (<20 Å). This process has been interpreted as the formation of granular aggregates that preserve a micropore network. This new arrangement of the aggregates produces a significant reduction in the free swelling volume.

Halloysite clay minerals are ubiquitous in soils and weathered rocks where they occur in a variety of particle shapes and hydration states. Diversity also characterizes their chemical composition, cation exchange capacity and potassium selectivity. This review summarizes the extensive but scattered literature on halloysite, from its natural occurrence, through its crystal structure, chemical and morphological diversity, to its reactivity toward organic compounds, ions and salts, involving the various methods of differentiating halloysite from kaolinite. No unique test seems to be ideal to distinguish these 1:1 clay minerals, especially in soils. The occurrence of 2:1 phyllosilicate contaminants appears, so far, to provide the best explanation for the high charge and potassium selectivity of halloysite. Yet, hydration properties of the mineral probably play a major role in ion sorption. Clear trends seem to relate particle morphology and structural Fe. However, future work is required to understand the possible mechanisms linking chemical, morphological, hydration and charge properties of halloysite.

The present paper shows the importance of Inverse Gas Chromatography (IGC) for the determination of the surface properties of bentonites. These properties are dispersive surface energy, acid-base properties, surface heterogeneity, sorption isotherms, BET surface areas and heat of sorption, using different probe molecules. IGC can contribute to the interpretation, prediction and optimization of the studied materials' properties. The paper focuses on two distinctive bentonite samples from Porto Santo Island, Madeira archipelago. In view of their potential value, achieved through their incorporation in products for dermopharmacy and dermocosmetics, particle size and particle surface properties are of fundamental importance.

The surfaces of fresh and tarnished (through exposure to the atmosphere) bornite have been studied by measurement of reflectance and quantitative colour parameters in the visible region, X-ray photoelectron and Auger electron spectroscopy, and conversion electron Mössbauer spectroscopy. The results of these studies, in combination with those of previous workers, indicate that a surface coating of an iron hydroxy-oxide forms on bornite, leaving beneath it a layer with a copper sulphide composition. A model to explain this alteration process is proposed based on a suggested surface reconstruction in bornite, leading to metals in essentially trigonal planar coordination. Resulting destabilization of iron relative to copper in this crystal chemical environment is suggested to account for its preferential oxidation.

The objective of this article is to evaluate the resistance to degradation of resin-dentin bonds formed with three one-step adhesives. Flat, mid-coronal dentin surfaces were bonded with the self-etching adhesives [Tokuyama Bond Force (TBF), One Up Bond F Plus (OUB), and G-Bond (GB)]. The bonded teeth were subjected to fatigue loading, chemical degradation, and stored in distilled water for four time periods (up to 12 months). Specimens were tested for microtensile bond strength and microleakage. Fractographic analysis was performed by scanning electron microscopy. Bonded interfaces were examined by light microscopy using Masson's trichrome staining. An atomic force microscope was employed to analyze phase separation and surface nanoroughness (Ra) at the polymers. Vickers microhardness and the degree of the conversion (DC) were also determined. ANOVA and multiple comparisons tests were performed. Bond strength significantly decreased after the chemical challenge, but not after load cycling. Aging decreased bond strength after 6 months in TBF and GB, in OUB after 12 months. An increase of the nonresin protected collagen zone occurred in all groups, after storing. TBF showed the highest roughness, microhardness, and DC values, and GB showed the lowest. Mild self-etch one-step adhesives (TBF/OUB) showed a higher degree of cure, lower hydrophilicity, and major resistance to degradation of resin-dentin bonds when compared to highly acidic self-etching adhesive (GB).

In the present study we report for the first time the presence of S-layer proteins in Lactobacillus kefir and Lactobacillus parakefir isolated from kefir grains. Soluble whole-cell protein profile obtained either by mechanical disruption (X-press) or by a combined treatment with lysozyme and SDS on whole cells, showed a significant band of apparent molecular mass of 66–71 kDa as measured by SDS–PAGE. The intensity of this band was considerably reduced when cells were treated with 5 M-LiCl. The above mentioned proteins were recovered in the LiCl extracts. After dialysis and concentration, the proteins extracted were able to reassemble in a regular array. Negative staining of these protein preparations were analysed by transmission electron microscopy and a paracrystalline arrangement was seen. Thin sections of bacteria analysed by transmission electron micrographs showed an outermost layer over the bacterial cell wall, that was lost after the LiCl treatment. The production of this surface structure under different culture conditions was also evaluated. Finally, the relationship between the presence of S-layer proteins and surface properties (e.g. adhesion to Caco-2 cells, autoaggregation, and hemagglutination) was investigated.

The total surface areas of human mastoid air cells were measured using digital CT scans. Using 24 normal ears, the lining of the mastoid air cells was digitally scanned, traced and analysed. The mean surface area of the mastoid air cell system was 167.0.cm2 and ranged from 74.78 to 330.01 cm2. The volume was also measured, the mean being 10.43.cm3 ranging from 6.25 to 20.52.cm3. The correlation coefficient between surface area and volume was 0.95. These results indicate that well pneumatized mastoid air cells serve to provide an extremely large surface area in the temporal bone which in normal mastoid air cells is proportional to the volume.