The aqueous chemistry of water films confined between clay mineral surfaces remains an important unknown in predictions of radioelement migration from radioactive waste repositories. This issue is particularly important in the case of long-lived anionic radioisotopes (129I-, 99TcO4-, 36Cl-) which interact with clay minerals primarily by anion exclusion. For example, models of ion migration in clayey media do not agree as to whether anions are completely or partially excluded from clay interlayer nanopores. In the present study, this key issue was addressed for Cl- using MD simulations for a range of nanopore widths (6 to 15 Å) overlapping the range of average pore widths that exists in engineered clay barriers. The MD simulation results were compared with the predictions of a thermodynamic model (Donnan Equilibrium model) and two pore-scale models based on the Poisson-Boltzmann equation under the assumption that interlayer water behaves as bulk liquid water. The simulations confirmed that anion exclusion from clay interlayers is greater than predicted by the pore-scale models, particularly at the smallest pore size examined. This greater anion exclusion stems from Cl- being more weakly solvated in nano-confined water than it is in bulk liquid water. Anion exclusion predictions based on the Poisson-Boltzmann equation were consistent with the MD simulation results, however, if the predictions included an ion closest approach distance to the clay mineral surface on the order of 2.0 ± 0.8 Å. These findings suggest that clay interlayers approach a state of complete anion exclusion (hence, ideal semi-permeable membrane properties) at a pore width of 4.2 ± 1.5 Å.

The Biga Peninsula of NW Turkey is host to many kaolin and halloysite deposits with mineralization occurring at the intersections of fault zones in contact with Late Eocene-Miocene calc-alkaline volcanic rocks. Distinguishing between the relative overprinting of hypogene by supergene processes in these deposits is a challenge and important because they affect the physical-chemical properties of minerals and their potential for industrial applications. This study examines the Sarıbeyli-Sığırlı and Bodurlar kaolin deposits in NW Turkey, which were formed from similar volcanics as evidenced by 40Ar/39Ar. Late Eocene (34.2 ± 0.20 Ma) to Early Oligocene (32.7 ± 0.17 Ma) ages for both primary volcanic rocks and alunites are consistent with surrounding rocks in the Çanakkale region. Criteria used to distinguish hypogene alteration from supergene alteration processes come from X-ray diffraction (XRD), Fourier-transform infrared (FTIR) and Raman spectroscopies, thermal gravimetric analysis (TGA), scanning and transmission electron microscopy (SEM, TEM), and elemental analyses. Isotopic δ18O depletion and δD enrichment of the Sarıbeyli-Sığırlı deposit suggests that it was more influenced by magmatic waters than was the Bodurlar deposit. The Bodurlar deposit contains a paucity of dickite compared to the Sarıbeyli-Sığırlı deposit, which is evidenced by lower TGA endotherms, higher ratios of XRD intensities for reflections at 1.316 Å and 1.307 Å, distinctive FTIR absorbance bands at 3620 cm− 1 and 3652 cm−1, and relative Raman intensities of the γ1 and γ5 vibrational modes.

A genetic model is proposed whereby these deposits are mainly formed through an acid-sulfate hydrothermal alteration, in what appears to be a volcanic-hydrothermal system. The extent of hydrothermal alteration was controlled by fault density and the initial texture of the volcanic rocks. These steam-heated environments included sulfide-enriched vapors and groundwater mixed to varying degrees in the vadose zone. The Sarıbeyli-Sığrlı and Bodurlar deposits, respectively, contain mineral assemblages that reflect both hypogene (kaolinite, alunite, dickite) and supergene (kaolinite, halloysite, jarosite) processes. These observations offer a basis for comparing and discriminating the relative influence of these two important alteration processes responsible for the formation of kaolin deposits in NW Turkey and around the world.

A rhamnolipid-layered double hydroxide (RL-LDH) nanocomposite, derived from the rhamnolipid (RL) biosurfactant, was synthesized through a delamination/reassembling process. The adsorption characteristics of Cu(II) on RL-LDH were investigated in detail and the results indicated the potential of using RL-LDH as an environmentally friendly adsorbent to remove Cu(II). The fabricated RL-LDH nanocomposite was characterized using powder X-ray diffraction, Fourier-transform infrared spectroscopy, scanning electron microscopy, transmission electron microscopy, elemental chemical composition, and specific surface area analyses. Batch adsorption experiments were conducted to study the influence of various factors, such as contact time, initial Cu(II) concentration, temperature, initial solution pH, and electrolyte concentration on Cu(II) adsorption by the RL-LDH nanocomposite. The RL-LDH nanocomposite had a low surface area of 11.71 m2 g−1, which suggests that surface adsorption would not be important in Cu(II) adsorption. The Cu(II) adsorption data fitted the Freundlich model well at pH 5.5, whereas the adsorption kinetics were accurately described by a pseudo-second-order kinetics model. Chemical binding, that is, the formation of a RL-Cu(II) complex in the LDH interlayer, was assumed to be the rate-limiting step in the adsorption process. Thermodynamic parameters that included Gibbs free energy, enthalpy, and entropy changes were also calculated. The adsorption was found to be a spontaneous and exothermic chemisorption process. Furthermore, the adsorption properties of RL-LDH for Cu(II) were compared to Cu(II) adsorption using other adsorbents.

A better understanding of the thermodynamics of radioactive cesium uptake at the surfaces of phyllosilicate minerals is needed to understand the mechanisms of selective adsorption and help guide the development of practical and inexpensive decontamination techniques. In this work, molecular dynamics simulations were carried out to determine the thermodynamics of Cs+ adsorption at the basal surface of six 2:1 phyllosilicate minerals, namely pyrophyllite, illite, muscovite, phlogopite, celadonite, and margarite. These minerals were selected to isolate the effects of the magnitude of the permanent layer charge (⩽2), its location (tetrahedral vs. octahedral sheet), and the octahedral sheet structure (dioctahedral vs. trioctahedral). Good agreement was obtained with the experiments in terms of the hydration free energy of Cs+ and the structure and thermodynamics of Cs+ adsorption at the muscovite basal surface, for which published data were available for comparison. With the exception of pyrophyllite, which did not exhibit an inner-sphere free energy minimum, all phyllosilicate minerals showed similar behavior with respect to Cs+ adsorption; notably, Cs+ adsorption was predominantly inner-sphere, whereas outer-sphere adsorption was very weak with the simulations predicting the formation of an extended outer-sphere complex. For a given location of the layer charge, the free energy of adsorption as an inner-sphere complex varied linearly with the magnitude of the layer charge. For a given layer charge location and magnitude, adsorption at phlogopite (trioctahedral sheet structure) was much less favorable than at muscovite (dioctahedral sheet structure) due to electrostatic repulsion between adsorbed Cs+ and the H atom of the OH- ion directly below the six-membered siloxane ring cavity. For a given layer charge magnitude and octahedral sheet structure, adsorption to celadonite (octahedral sheet layer charge) was favored over adsorption to muscovite (tetrahedral sheet layer charge) due to the increased distance to the surface K+ ions and the decreased distance to the O atom of the OH- ion directly below the surface cavity.

The structures of Fe-rich chlorite and berthierine and the formation mechanisms of 7 Å–14 Å interstratified minerals were not previously fully understood owing to the difficulties in analyzing them by X-ray diffraction (XRD). The present study characterizes Fe-rich chlorites in quartz veins of epithermal to xenothermal vein-type ore deposits without later structural modifications, based on high-resolution transmission electron microscopy (HRTEM) along with XRD examination and chemical analysis. Samples have a wide range of Fe/(Fe+Mg) ratios from 0.38 to 0.98 and tetrahedral Al substitution for Si from 0.94 to 1.44 atoms per formula unit (apfu). The variation in Fe content nearly parallels the tetrahedral Al content. The formation temperatures estimated by chlorite geothermometry range from 190°C to 320°C. In HRTEM, most of the samples showed interstratification between 7 Å, 14 Å, and/or (in some samples) smectite layers. Chlorites with relatively low Fe contents (Fe/(Fe+Mg) ≈ 0.4) were characterized by mostly 14 Å periodicity with the polytype IIbb. In contrast, interstratification of 7 Å and 14 Å layers predominated with increasing Fe content and the proportion of 7 Å layers exceeds 80% in Fe-rich samples with Fe/(Fe+Mg) > 0.9. The 7 Å component layer approximated Fe-rich berthierine based on the chemical composition. Layer stacking structures in the Fe-rich samples were complex, and characterized by disorder of 7 Å and 14 Å layers, differences in the polarity of the tetrahedral sheets, variations of the slant of the octahedral sheets, and positional disorder between octahedral and tetrahedral sheets involving the hydrogen bonding, as indicated from HRTEM observations along the Yi directions of the phyllosilicates. The complex stacking structures observed in Fe-rich samples suggest that irregularity was controlled by neither the Fe/(Fe+Mg) ratio nor the formation temperature; stacking was controlled by kinetic factors in the process of mineral precipitation under disequilibrium conditions.

In some real and up-scale tests using high-level radioactive waste (HLRW), Mg accumulation was observed in smectites at the contact of heated Fe or Cu metal tubes. It is important to understand why Mg accumulated in order to model the long term performance of bentonites in HLRW systems. In some of these tests, an increased number of trioctahedral domains was measured in the smectites using X-ray diffraction (XRD) and infrared spectroscopy (IR). The trioctahedral domains either formed by the dissolution/precipitation of smectites or by the addition of Mg through a solid-state reaction similar to the Hofmann-Klemen effect. The Hofmann-Klemen effect is used in the Greene-Kelly test to distinguish montmorillonites from beidellites. Many studies have been carried out about Li-uptake by smectites, but Mg was rarely taken into account. The present study was, therefore, undertaken to compare the interactions of different bentonites with Li and Mg under various conditions. A significant CEC decrease was found for Li- and Mg-saturated bentonite samples after heating at 250°C under dry conditions. The extent of this CEC reduction depended on the octahedral to tetrahedral charge ratio and was smaller for Mg-saturated samples than Li-saturated samples. This finding proved that it is much more difficult for Mg to enter octahedral vacancies than Li, which probably can be explained by the larger hydration energy and/or slightly larger radius of Mg. The relationship between CEC reduction and the octahedral/tetrahedral charge ratio of both Li- and Mg-saturated samples, however, suggests a similar process. The Mg that can reside at the bottom of the pseudohexagonal holes would not explain this relationship. The important result with respect to understanding HLRW bentonite performance, on the other hand, is that Mg fixation only occurs under dry conditions and that Mg fixation acts as a sink for Mg and, hence, leads Mg to diffuse towards the heated metal surface.

Sepiolite and palygorskite are common as layers and nodules in the Neogene lacustrine sediments of the Eskişehir area. This study aims to determine their mineralogical and geochemical characteristics, plus the distribution of these economically important sepiolite and palygorskite deposits within the lacustrine environment. Using these data the research goes on to discuss the environmental conditions for their formation. Sepiolite and palygorskite layers are associated with dolomite, marlstone, and argillaceous limestone. The sepiolite nodules (meerschaum), which are former magnesite gravels, are observed in the Upper Miocene reddish-brown fluvial deposits derived from the ophiolite and its fractureinfills at the northern margin of the basin. Sepiolite and palygorskite are only sparsely associated with dolomite and accessory magnesite, quartz, feldspar, and amphibole. Sepiolite and palygorskite fibers formed as oriented platy fan, interwoven, and knitted aggregates in the absence of dolomite indicated precipitation from supersaturated solution. Sepiolite and palygorskite fibers edging dolomite crystals postdate dolomite and formed through precipitation in a vadose environment under semi-arid to arid climatic conditions. High values of Mg+Fe+Ni and enrichment of light rare earth elements (LREE) relative to middle rare earth elements (MREE) and heavy rare earth elements (HREE), Sr content, depletion of Rb+Ba and K, and negligible negative Eu anomalies all reflect the derivation from the Paleozoic metamorphic and Upper Cretaceous ophiolitic rocks. Locally, Upper Miocene to Lower Pliocene volcanic, volcanoclastic, and fluvio-lacustrine sedimentary rocks supplied the required Si, Mg, Al, and Fe for precipitation of Al-sepiolite and Mg-palygorskite with average structural formulae of Si11.91Al0.09O30Mg6.60Al0.78Fe0.13 (OH)4Na0.12K0.06(OH2)4·nH2O and Si7.74Al0.26O20Mg2.52Al1.13Fe0.38(OH)2(OH2)4Na0.32K0.14 Ca0.12·nH2O, respectively. In contrast to the layered sepiolites, the absence of Al and high Ni content in sepiolite nodules suggest formation through replacement of magnesite gravels at shallow burial in an alkal ine environment. The calculated meerschaum sepiol ite chemical formula i s: Si12.02O30Mg7.87Fe0.01(OH)4Na0.13K0.03(OH2)4·nH2O.

The influence of anionic dispersing agents, such as sodium poly(acrylic acid), sodium hexametaphosphate, and sodium silicate on the dissolution of crude kaolin was examined by measuring the dissolved metals produced in the absence and presence of dispersing agents. For this purpose, the rheological and structural changes caused by the dissolution of kaolin metal constituents were studied in batch mode using several parameters, namely, solids (wt.%), pH, contact time (aging), and dispersing agent dose. A noteworthy increase in kaolin dissolution was caused by the presence of dispersing agents, particularly poly(acrylic acid) and sodium hexametaphosphate. These agents produced conspicuously large amounts of dissolved Al in comparison to the other experimental treatments. Little dissolved Si was measured under similar conditions in distilled water, but the amount of Si released using dispersing agents was nearly double that observed in distilled water only. Excess dispersing agents interacted with kaolin and dissolved accessory elements in the kaolin (i.e. Fe, Ca, Mg) and thus released enough Fe to form a stable Fe—dispersant complex. The present study showed that this phenomenon also contributed to a significant increase in the release of dissolved Al and Si through complexation.

A modified procedure for bentonite purification and a new method for the quantitative characterization of bentonite using smectite content are reported. Bentonite found in a drill core of Tsunagi Mine, Niigata, Japan was evaluated by the new method to demonstrate the substantial increase in smectite content from 40% in the original bentonite to 75% after purification using a new procedure. Powder samples were prepared by putting blocks of bentonite into acetone to remove water without mechanical crushing. The powdered, acetone-dried bentonite was purified by a dispersion-sedimentation method in water after cation exchange of the interlayer Ca2+ ion with Na+ ion by the reaction of raw bentonite with aqueous NaCl. The purification was evaluated using X-ray diffraction and thermogravimetric analyses (TG). The raw bentonite contained feldspar, quartz, and cristobalite, and feldspar and quartz were removed by the new purification procedure. The purification was evaluated quantitatively by comparing the TG data before and after the purification. The purified bentonite swelled in water to give a stable aqueous suspension and 3 g of purified bentonite dispersed in 60 mL of water was stable for several days. The replacement of interlayer sodium with dibehenyldimethylammonium gave an organophilic clay, which swelled in toluene. The bentonite has potential practical uses as a purified bentonite and an organophilic bentonite.

A detailed structural characterization of organo-clays is a key in understanding their properties. In this work, mono-, di-, tri-, and tetra-butylammonium (nBA; n = 1–4) cations intercalated in the layered clay mineral montmorillonite (Mnt) have been studied for the first time by combining a theoretical approach based on density functional theory (DFT) and infrared spectroscopy. The DFT calculations revealed the detailed structure and position of nBA cations in the interlayer space. A relation between the basal spacing (d001 parameter) and the cation size and structure was found, and explained with respect to the structure, composition, and size of the organic cations. Hydrogen bonds between -NHx/-CH3/-CH2 groups of the nBA cations and oxygen atoms of the basal planes of the Mnt layers were found to be an important factor for the arrangement and energetic stabilization of cations in the interlayer space. The N-H-O hydrogen bonds are stronger than C-H-O hydrogen bonds and the stabilization decreases with decreased number of bands. Analysis of DFT-calculated vibrational modes helped in understanding a problematic region of the experimental infrared spectra (4000–3000 cm-1), in which assignment of all vibrational modes unambiguously was not possible because of a significant overlap of broad bands.

The potential of near-infrared (NIR) spectroscopy to track the adsorption of water on montmorillonite saturated with different exchangeable cations is demonstrated in the present study. The Na+, K+, Ca2+, and Mg2+ forms of JP montmorillonite (Jelšový Potok, Slovakia) were first dried and then hydrated at 23, 52, 88, and 100% relative humidity (RH). The combination band of water molecules, $(\nu +\delta {)}_{H_{2}O}$$\end{document}, allowed the study of the effect of exchangeable cations on the strength of H bonds between water molecules and on the amount of adsorbed water. With increasing ionic potential (IP) of the exchangeable cation, the strength of the H bonds increased and the $(\nu +\delta {)}_{H_{2}O}$\$\end{document} band was shifted to lower wavenumbers. The area of the $(\nu +\delta {)}_{H_{2}O}$\$\end{document} band, corresponding to the amount of adsorbed water, was compared with results from gravimetry. The good correlation (R2 > 0.97) between the two independent methods confirmed that the $(\nu +\delta {)}_{H_{2}O}$\$\end{document} band area reflected reasonably well the amount of H2O in montmorillonite. The peak-fitting analysis of the $(\nu +\delta {)}_{H_{2}O}$\$\end{document} band allowed differentiation of weakly and strongly H-bonded water molecules. The position of the high-frequency component at 5260–5250 cm−1, related to H2O weakly H-bonded to basal oxygens of the tetrahedral sheets, was influenced only slightly by the exchangeable cations. Two low-frequency components were assigned to the combination modes involving asymmetric (ν3) and symmetric (ν1) stretching vibrations of strongly H-bonded H2O. Only the $({\nu }_1+\delta {)}_{H_{2}O}$\$\end{document} component (5055–5000 cm−1) showed significant dependence on the type of exchangeable cation and hydration level. Peak-fit analysis revealed a small effect of the type of exchangeable cation on the amount of water molecules weakly H-bonded to the siloxane surface but a pronounced effect on the content of strongly hydrogen-bonded H2O. The amount of weakly H-bonded H2O remained stable after reaching a certain level of hydration, but a gradual increase in the strongly H-bonded water molecules with increasing RH was observed.

Aluminum substitution is a common phenomenon in environmental iron oxides and oxyhydroxides, affecting the color, magnetic character, surface features, etc. Several methods for preparing Al-substituted iron oxyhydroxides can be found in the literature, resulting in samples with particular properties. In the present study, the synthesis of aluminum-substituted goethites, AlxFe1-xOOH with 0 ⩽ x ⩽ 0.15, by homogeneous precipitation and the transformation to aluminum-substituted hematites, (AlxFe1-x)O3, are presented. The goethite samples were produced at 90°C from solutions of urea and iron and aluminum nitrates in the presence of ammonium sulfate (GU series). Although attempts were made to incorporate up to 33 mole% of Al into the goethite, only ~15 mole% was found to be within the structure, due to the final pH, ~7, of the synthesis. Another feature of these goethites was a lateral alignment of the tabular particles. By heating batches of the GU samples at 400°C and 800°C, two series of Al-hematites were obtained, denoted here as the HX400 and HX800 samples, respectively. X-ray diffraction, thermal analysis, Karl-Fischer titration, transmission electron microscopy, and Mössbauer spectroscopy were used to characterize the samples. The X-ray patterns showed the samples to be pure iron phases, with particle sizes of ~10 nm for the GU and HX400 samples, and of ~70 nm for the HX800 samples. An inversion in the intensities of the (104) and (110) diffraction peaks of hematite was observed to be dependent on the aluminum substitution and was explained by small particle sizes, shape anisotropy, and the presence of nanopores. The cell parameters of both GU and HX samples showed a small decrease with increasing aluminum substitution up to x ≈ 0.15. The amount of adsorbed sulfate, presumably as an aluminum hydroxy sulfate gel, increased with aluminum substitution in all GU and HX samples, reaching a maximum of ~6.5 wt.% for the highest substitution. Heating at 100°C did not remove all of the adsorbed water, and significantly higher temperatures were required to achieve complete removal. Mossbauer spectra at 295 K and 80 K are typical for small-particle goethite and hematite, and revealed that Al-for-Fe substitution in all samples seems to be limited to ~15 mol.%.

The aim of the present study was to discriminate between distinct types of clay units by applying multivariate statistical techniques, which have seldom been applied to the exploitation of ceramic clays. At the outcrop scale, texturally similar argillaceous or clayey layers of different ceramic types cannot be effectively distinguished, which can result in the misuse and loss of raw materials. Representative samples of clayey raw materials from central Portugal Cenozoic deposits with potential use in the manufacture of structural clay products were first assessed for granulometric, mineralogical, chemical, and technological properties. Based on those properties and the use of multivariate statistical techniques, i.e., factor analysis (FA) and cluster analysis (CA), a novel statistical approach that combined all these variable properties was produced. This approach made it possible to distinguish the ceramic suitability and perceive which parameters most influence that suitability. The use of R-mode FA made it feasible to differentiate and group samples based on the most influential variables: the contents of Al2O3, Fe, illite, quartz, feldspars, and K2O. The use of R-mode CA substantiated the FA results in the identification of influential variables, such as Al2O3, Fe, and illite. The use of Q-mode CA established two main clusters: clayey-silt samples and sandy and/or feldspathic samples, the clayey-silt samples encompassed three sub-clusters. These three sub-clusters match ceramic types with different suitabilities and relate sample stratigraphic setting to the encompassing stratigraphic units. Diagrams that relate the grain size, the content of different oxides, the content of different minerals, and the plasticity to the ceramic suitability illustrate the CA groupings. An adequate blend of sand and clay for red stoneware (bricks and tiles) manufacture was indicated as a major requirement for most raw materials of the clayey-silt cluster. Raw materials represented by the sandy and/or feldspathic cluster can either be used to blend with materials that lack sand or to blend with excessively plastic samples.

Reflectance spectroscopy is a rapid and non-destructive method that can be used to detect organic compounds in geologic samples over a wide range of spatial scales that includes outcrops, hand samples, drill cores, and planetary surfaces. In order to assess the viability of this technique for quantification of organics and aliphatic compounds in particular, the present study examines how clay mineralogy, water content, and albedo influence the strength of organic absorptions in near-infrared (NIR) reflectance spectra. The effects of clay structure and water content are evaluated using kaolinite, smectite (montmorillonite), and a mixed-layer illite-smectite as starting materials. Absorption strengths for C—H absorptions are compared to known total organic carbon (TOC) values using both reflectance spectra and single scattering albedo (SSA) spectra derived from a Hapke radiative transfer model. A linear relationship was observed between band depth and TOC for each sample suite, but strong albedo variation led to non-unique trends when band depths were calculated from reflectance spectra. These effects were minimized by conversion to SSA, for which band depth-TOC trends were similar for all mixture suites regardless of albedo or hydration level, indicating that this approach may be more broadly applicable for clay and organic-bearing samples. Extrapolation of band depth-TOC trends for the synthetic mixtures suggested a very conservative lower limit of detection of <1 wt.% TOC, but preliminary results for natural organic-bearing shales indicated that detection limits may be an order of magnitude lower.

Some aspects of the crystal structure of illite are not understood properly yet, in spite of its abundance and significance as a component of soils, sediments, and low-grade metamorphic rocks. The present study aimed to explore the role of hydronium cations in the interlayer space of illite in a theoreticalexperimental approach in order to clarify previous controversial reports. The infrared spectroscopy of this mineral has been studied experimentally and by means of atomistic calculations at the quantum mechanical level. The tetrahedral charge is critical for the stability of the hydronium cations, the presence of which has probably been underestimated in previous studies. In the present study, computational studies have shown that the hydronium cations in aqueous solutions are likely to be intercalated in the interlayer space of illite, exchanging for K cations. During the drying process these cations are stabilized by hydrogen bonds in the interlayer space of illite.

The results from mesoscale simulations of the formation and evolution of microstructure for assemblies of Na-smectite particles based on assumed size distributions of individual clay platelets are presented here. The analyses predicted particle arrangements and aggregation (i.e. platelets linked in face—face configurations) and are used to link geometric properties of the microstructure and mechanical properties of the particle assemblies. Interactions between individual ellipsoidal clay platelets are represented using the Gay-Berne potential based on atomistic simulations of the free energy between two Na-smectite clay-platelets in liquid water, following a novel coarse-graining method developed previously. The current study describes the geometric (aggregate thickness, orientation, and porosity) and elastic properties in the ‘jammed states’ from the mesoscale simulations for selected ranges of clay particle sizes and confining pressures. The thickness of clay aggregates for monodisperse assemblies increases (with average stack thickness consisting of n = 3–8 platelets) with the diameter of the individualclay platelets and with the level of confining pressure. Aggregates break down at high confining pressures (50–300 atm) due to slippage between the platelets. Polydisperse simulations generate smaller aggregates (n = 2) and show much smaller effects of confining pressure. All assemblies show increased order with confining pressure, implying more anisotropic microstructure. The mesoscale simulations are also in good agreement with macroscopic compression behavior measured in conventional 1-D laboratory compression tests. The mesoscale assemblies exhibit cubic symmetry in elastic properties. The results for larger platelets (D = 1000 Å) are in good agreement with nano-indentation measurements on natural clays and shale samples.

Surface and groundwaters become contaminated with dyes due to discharge into the environment, which increases the risk of a number of human diseases. Many methods of dye removal from discharge waters at the source have been developed, but few are effective and the most effective method (activated carbon) is very expensive. The purpose of the present study was to test a natural zeolite (clinoptilolite type) as a potentially effective and inexpensive method to remediate dye discharge into the environment. In the removal experiments, malachite green (MG) and rhodamine B (RB) cationic dyes were used. The effects of various experimental conditions such as initial dye concentration, pH, and temperature on dye removal were investigated in a single-dye system. The degree of removal of MG and RB increased with increasing initial concentration and temperature of the dye in a single-dye system. An increase in pH decreased RB removal, but increased MG removal. In a two-dye system, MG and RB adsorption decreased by ~41.74 and 21.51%, respectively, due to competitive adsorption of the two dyes. Adsorption reflected a pseudo-second order kinetics model with high correlation coefficients (r2 = 0.996–1.000) in single-dye and two-dye systems. Adsorption was most consistent with the Langmuir-1 and the Redlich-Peterson isotherm models with high correlation coefficients (r2 = 0.987–0.999) in both systems. The Langmuir-1 adsorption capacities were determined as 43.86 and 44.25 mg/g for the removal of MG and RB in single-dye systems, respectively. In a two-dye system, the Langmuir-1 capacities were 20.62 and 31.54 mg/g for the removal of MG and RB, respectively.