A comparative crystallochemical study was performed on natural and synthetic hydrotalcite-like compounds with similar compositions. The nature of the brucite-like sheet stacking was addressed by means of powder X-ray diffraction. From the resulting electron diffraction patterns it was possible to establish the order-disorder of the cations in the brucite-like sheet. The results show that a natural sample from Snarum is an intergrowth of hydrotalcite (3R1 polytype) and manasseite (2H1 polytype) at a ratio of 77:23 (wt.%). An aluminian serpentine is associated with the hydrotalcite and manasseite minerals. The structure of a synthetic sample, Mg:Al = 2:1, was determined as space group $R\overline{3}m$. For a few crystals in this sample, the octahedral cation distribution is compatible with the observed supercell (a = a′ √3). A second synthetic sample showed the presence of stacking faults and was described as a random layer sequence of two polytypes (3R and 2H).

Reduced-charge samples were prepared from Li+- and Ni2+-saturated SAz-1 montmorillonite by heating at 150 and 300°C for 24 h. X-ray diffraction analysis showed interstratification of non-swelling and swelling interlayers in LiS150, while fully expandable interlayers were found in NiS150. Heating at 300°C caused collapse of the interlayers in LiS300 in contrast to NiS300, for which some expandable layers were interstratified in the pseudo-pyrophyllite structure. The infrared (IR) spectra of heated Li-SAz showed new OH-stretching and overtone bands near 3670 cm−1 and 7170 cm−1 (1395 nm), respectively, indicating creation of local trioctahedral domains containing Li(I) in the previously vacant octahedra. No evidence of OH groups in trioctahedral coordination was found in the spectra of heated Ni-SAz. Nickel is supposed to be trapped in the hexagonal holes of the tetrahedral sheets. Reduction of the layer charge substantially affected the extent of the dissolution of SAz-1 montmorillonite in HCl. The MIR and NIR spectra of unheated Li- and Ni-SAz showed a substantial degradation of their structure after acid dissolution. New bands observed at 3744 cm−1 and 7314 cm−1 (1367 nm) were assigned to the vibrations of Si-OH groups formed upon acid treatment. These bands are a means of checking the extent of acid attack on smectites, even in cases when no differences are observed in the 1300−400 cm−1 spectral region (traditionally used to monitor this process). Both the IR spectra and solution analysis revealed that development of non-swelling interlayers in heated montmorillonites substantially reduced dissolution of these samples. The results obtained confirmed that acid attack of the smectite structure occurred at both interlayer surfaces and edges. If the accessibility of the layers for protons is low due to non-swelling interlayers, the dissolution was slower and took place mainly from the particle edges.

The adsorption of the herbicides quinmerac 7-chloro-3-methylquinoline-8-carboxylic acid (QMe) and quinclorac 3,7-dichloroquinoline-8-carboxylic acid (QCl) on homoionic Fe3+-, Al3+-, Cu2+-, Ca2+-, K+- and Na+-exchanged montmorillonite was studied in aqueous solution. Adsorption data were fitted to the logarithmic form of the Freundlich equation. Ca- and Na-exchanged montmorillonites were ineffective in the adsorption of QMe. On the other hand, the QMe adsorption on Fe-exchanged montmorillonite was rapid and the equilibrium was attained after 15 min. An H-type isotherm was observed for the QMe adsorption on Fe-clay, indicating a high affinity of the solute for the sorption sites and almost complete adsorption from dilute solution. On the other hand, the adsorption isotherm of QMe on Al- and K-clay was of the S-type. This shape suggests that the solvent molecules may compete for the sorption sites. A Fourier transform infrared (FTIR) study suggested that the adsorption mechanism of QMe on Fe-, Al- and K-clay involves the protonation of QMe molecule due to the acidic water surrounding the saturating cations. The greater acidity of Fe-clay compared with Al- and K-clay explains both the lower QMe adsorption observed on Al and K systems and the lack of adsorption on Na and Ca systems. In contrast, the formation of a Cu complex permitted QMe to be adsorbed to a large extent to Cu-clay as shown by FTIR analysis. The QCl was adsorbed only by Fe-clay and the adsorption isotherm of QCl on Fe clay was of the S-type. This finding is consistent with the lower basic character of the QCl molecule nitrogen. In fact, the replacement of the electron-releasing methyl group in QMe with an electron-withdrawing Cl atom to form QCl makes the nitrogen lone-pair electrons of the quinoline ring unavailable for either protonation or complexation.

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 organoclay quasicrystals formed by exchange reactions of fluoromagnesian smectite (FMS) and two kinds of cationic surfactants were investigated by X-ray diffraction (XRD) of both aqueous suspensions and dried powders. ζ potential measurements were also carried out. The two cationic surfactants employed in this study, dodecyltriphenylphosphonium bromide (C12PBr) and dodecyltrimethylammonium bromide (C12NBr), have the same alkyl chain length but different head group structures. In aqueous suspensions of C12N/FMS, regular stacking with a basal spacing of 2.28 nm was observed within the range 0.4 to 1.0 of the cation exchange capacity (CEC) of the C12N/FMS ratios. The basal spacing was constant in this range. The most intense diffraction for the C12N/FMS suspension was observed at 0.6 CEC, and a further increase in the C12N/FMS ratio resulted in a decline of the diffraction intensity and a slight increase in the peak width. On the other hand, in C12P/FMS suspensions with the surfactant/FMS ratios <0.6 CEC, only weak, broad XRD peaks were observed. With higher C12P/FMS ratios (0.8 and 1.0 CEC), strong diffraction peaks appeared with a basal spacing of 3.20 nm. The difference in the observed basal spacings of C12N/FMS and C12P/FMS tactoids was ∼0.9 nm, which did not agree with the difference in the estimated height of the two surfactants (∼0.1 nm). These differences of the tactoid structures between C12N/FMS and C12P/FMS suspensions could be explained in terms of the difference in the adsorption manner of the surfactants on the silicate surface and in the size of the surfactant head groups.

The intercalation of a saponite with the Al polycation [Al13(OH)24(H2O)24]15+ is described. This polycation is obtained by reaction of alumina with Al chloride. The intercalation is achieved by reaction of very concentrated solutions of this polycation with the clay in powder form. Solids with a basal spacing of 18.9 Å were obtained in this way, stable up to 700°C (17.0 Å). The Langmuir surface area of the intercalated solid was 366 m2/g, and that value decreases to 119, 138 and 125 m2/g for the solids pillared at 500, 600 and 700°C, respectively.

The adsorption behavior of quaternary ammonium cationic surfactants with different hydrocarbon chain lengths, i.e. HDTMA (hexadecyltrimethylammonium), TDTMA (tetradecyltrimethylammonium) and DDTMA (dodecyltrimethylammonium), onto clinoptilolite has been investigated. The adsorption isotherms of these surfactants are correlated with the ζ potential curves of clinoptilolite. Accordingly, the applicability of the hemimicelle hypothesis to the adsorption of cationic surfactants at the clinoptilolite/water interface considering in the electrical double layer (EDL) of clinoptilolite is discussed. Even though the adsorption occurs in the EDL of clinoptilolite, the adsorption of HDTMA, TDTMA and DDTMA onto clinoptilolite is not conveniently described by the hemimicelle hypothesis. The absence of all expected marked increase in the ζ potential curves at the hemimicelle concentration is ascribed to the large external cation exchange capacity of clinoptilolite. The hydrocarbon chain length of surfactant molecules is found to have a significant effect on the ion exchange as well as hydrophobic interaction mechanisms. The effectiveness of both ion exchange and hydrophobic interactions increases with increasing chain length, and so the greatest surfactant adsorption onto clinoptilolite was obtained by HDTMA.

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 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.

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.

Clay minerals appear to change significantly under the influence of pasture development on poldered sediments in the Baie d'Authie area (Somme, France). Cores 40–90 cm deep from recent salt marsh sediments and poldered sediments developing grass pastures since 1737, 1575 and 1158 indicate that the natural mineral suite of kaolinite, mica, illite, and two disordered mixed-layered illite-smectite (I-S) phases common to the sedimentary input changes gradually but significantly in the materials. In the oldest, best-developed profile, there is a dominance of a disordered, illitic I-S in the humic upper part of the profile and a more abundant, more smectitic I-S mineral below. It appears that grass-derived humic materials tend to stabilize closed (collapsed) or illitic behavior in I-S clays. The natural evolution of the sediment (lower part of the profile) is towards a smectitic clay assemblage. Destruction of organic matter of the smectitic I-S minerals by oxidation indicates that this material can significantly modify the physical behavior of the clays keeping the structure open to polar molecules.

This paper describes an improved simple, sample-mounting method for random powder X-ray diffraction (XRD), namely the razor tamped surface (RTS) method, which prepares a powder mount by tamping the loose powder with the sharp edge of a razor blade. Four kaolinites and a quartz powder were used to evaluate the RTS method by quantifying the degree of orientation in the sample mounts using orientation indices. Comparisons between the RTS and other published simple methods, consisting of front loading, back loading and side loading, indicate that the RTS method produces minimum packing density and minimum preferred orientation in the powder mounts of all five samples. The quartz powder used in this study does exhibit a tendency to preferred orientation. The mechanism by which the RTS method reduces preferred orientation is examined by comparing the width of the sharp blade edge with the size of clay particles. The advantages and disadvantages of the RTS method are also discussed.