Heterostructures formed by nanoparticles hybridized with porous hosts are of great potential in many practical applications such as catalysis, adsorption, and environmental remediation, based on their intrinsic properties. The objectives of this study were to synthesize zerovalent iron nanoparticles/montmorillonite heterostructures and to investigate their textural evolution under different Fe loadings. Iron nanoparticles were hybridized with montmorillonite by impregnation of montmorillonite by ferric ions followed by chemical reduction with sodium borohydride in solution. These hybridized Fe nanoparticles were well dispersed on the montmorillonite surface, size adjustable, and resistant to oxidation under the protection of native Fe-oxide shells. The textural evolution of these heterostructures under various Fe loadings was investigated using nitrogen physisorption, X-ray diffraction, electron microscopy, and elemental analyses. As the Fe loadings increased, the total pore and mesopore volumes were almost unchanged; the total, micropore, and external surface areas as well as the micropore volume decreased; and the average pore diameter increased. These textural changes could be attributed to the filling of the interparticle pores of montmorillonite by a variable amount of Fe nanoparticles. In addition, with increasing Fe loadings, the mesoporous character was enhanced for these heterostructures. These fundamental results are important in understanding the structure of these heterostructures as well as in developing some novel applications in related fields.

The industrial assessment of ceramic clays commonly consists of the determination of just two parameters, the particle-size distribution and the chemical composition; other parameters may also be important, however. The aim of the present study was to show that a careful determination of the mineralogical phase content provides valuable additional information on the processing behavior of ceramic clays.

Two ceramic clays (W1 andW2) from theWesterwald area, Germany, were evaluated as being the same with respect to industrial screening criteria, but showed different processing properties. In order to elucidate the different behaviors, both clays were investigated comprehensively using a multi-method approach combining physical-chemical and mineralogical methods.

Different aggregation characteristics for the two clays were revealed by determining the grain-size distribution with and without Na-pyrophosphate as a dispersant. In addition, W1 showed a greater electrical conductivity and soluble-salt concentration which promoted dispersion behavior.

The phase content was identified both for bulk materials and for several grain-size fractions by X-ray diffraction (XRD) and Rietveld analysis. The quantitative phase content was crosschecked with the chemical composition by X-ray fluorescence (XRF) analysis. Additional information was gathered by thermal analysis, cation exchange capacity (CEC) measurements, Mössbauer spectroscopy, and optical microscopy. While bulk samples of W1 and W2 showed nearly the same mineralogical and chemical compositions, investigation of the clay-size fractions (0.6–2 μm, <0.6 mm) revealed differences in the composition of the 2:1 layer silicates. The percentages of smectite in the mixed-layer I-S, as well as the amount of kaolinite, discrete illite, and smectite were determined by one-dimensional XRD profile fitting (ODPF). Best-fitting results for W1 were achieved for a physical mixture of an illite-rich I-S mixed-layer mineral (R3 I(0.9)-S) with discrete smectite, whereas W2 was characterized by a greater proportion of smectite in the mixed-layer (R1 I(0.8)-S), without discrete smectite. Based on the different structural features of the swellable clays, a qualitative delamination model for the 2:1 layer silicates during processing of the clays was derived. The model provides a further approach, aside from aggregation characteristics, to help understand the clay-processing behavior, which was found to be different for the two ceramic clays investigated.

The polymer model provides a relatively simple and robust basis for estimating the standard Gibbs free energies of formation (ΔGfo) and standard enthalpies of formation (ΔHfo) of clay minerals and other aluminosilicates with an accuracy that is comparable to or better than can be obtained using alternative techniques. The model developed in the present study for zeolites entailed the selection of internally consistent standard thermodynamic properties for model components, calibration of adjustable model parameters using a linear regression technique constrained by ΔGfo and ΔHfo values retrieved from calorimetric, solubility, and phase-equilibrium experiments, and assessments of model accuracy based on comparisons of predicted values with experimental counterparts not included in the calibration dataset. The ΔGfo and ΔHfo predictions were found to average within ±0.2% and ±0.3%, respectively, of experimental values at 298.15 K and 1 bar. The latter result is comparable to the good accuracy that has been obtained by others using a more rigorous electronegativity-based model for ΔHfo that accounts explicitly for differences in zeolite structure based on differences in framework density and unit-cell volume. This observation is consistent with recent calorimetric studies indicating that enthalpies of transition from quartz to various pure-silica zeolite frameworks (zeosils) are small and only weakly dependent on framework type, and suggests that the effects on ΔHfo of differences in framework topology can be ignored for estimation purposes without incurring a significant loss of accuracy. The relative simplicity of the polymer model, together with its applicability to both zeolites and clay minerals, is based on a common set of experimentally determined and internally consistent thermodynamic properties for model components. These attributes are particularly well suited for studies of the effects of water-rock-barrier interactions on the long-term safety of geologic repositories for high-level nuclear waste (HLW).

The layer charge density (LCD) of montmorillonite represents the permanent negative charge, its most important property. The LCD can be determined by two different methods, the structural formula method(SF M) and the alkylammonium method (AAM). Other methods of determining the LCD are calibrated against one or the other of these. The results of the two methods differ systematically: SFM values are larger than AAM values and the difference increases with increasing layer charge density. In the present study, the critical parameters of both methods were considered quantitatively in order to identify the most likely reason for the systematic difference. One particularly important argument against the validity of the SFM is that typical SFM values correspond to unrealistically large CEC values that have never been reported. In addition, SFM does not consider the variable charge which causes cations to be adsorbed to the outer surface (at pH >4). In contrast to minor constituents, which can of course also affect SFM values, the variable charge can explain only part of the systematic difference. The exchange of pure smectite samples with both Cu-trien andalkyla mmonium revealedthe presence of non-exchangeable, nonstructural cations (Na, K, Ca). These cations, together with 10% (or more) variable charge, may explain the differences in LCD values. The non-exchangeable, non-structural cations could stem from undetected traces of feldspar or volcanic glass. The present samples indicated that the systematic difference in LCD values between the two methods is related to the amount of non-exchangeable, non-structural cations only, indicating that the two LCD methods probe different features of smectites. Using the SFM on pure smectite provides a value for the total number of charges (permanent with andwithout fixed (= non-exchangeable, non-structural) cations plus variable charge). The AAM, on the other hand, provides the charge density of the exchangeable cations (without variable charge).

The objectives of this study were to investigate the effects of chemical parameters on the characterizationof W-type zeolite crystals and their intergrowths with other types of zeolites. The crystal size and purity ofW-type zeolites are affected significantly by the gel composition with respect to the molar ratios of SiO2/Al2O3 (aluminosilicate module, α), H2O/K2O (alkainity, β), and water content (H2O/SiO2, γ). The effects of these gel parameters ont he synthesis and characterizationof W-type zeolite were investigated.

Crystalline W-type zeolite of high purity was synthesized using a gel with a molar ratio of Al2O3:6.4SiO2:5.6K2O:164.6H2O at T = 165°C for a period of 72 h. The effect of excess K2O/SiO2 ratio ina mono-cation (K)-SiO2-Al2O3 gel-composition system on the nanoparticle size and purity of the product was also investigated. Experiments were carried out using the following levels of alkalinity: 21.4, 29.4, and 51.9; aluminosilicate module: 5.0, 6.4, and 10.0; water content: 16.5, 25.7, and 32.9; and excess K2O/SiO2 ratio: from 0.65 to 3.33. The results showed that by increasing the aluminosilicate module at high K2O/SiO2 ratio, the crystallinity and crystal size of the zeolite synthesized increased, while at low alkalinity, the crystallinity and crystal size decreased. Decreasing alkalinity at low aluminosilicate module increased the crystallinity and decreased the crystal size, while at high aluminosilicate module, both decreased. Finally, by increasing the water content at all aluminosilicate module and alkalinity values, the crystallinity and crystal size of the W-type zeolite increased. Excess K2O/SiO2 ratio was the key factor that should be adjusted int he range 0.7–1.0 for synthesis of pure crystals of W-type zeolite.

Kaolinite is often a cause of deformation in soft-rock tunnel engineering, leading to safety problems. In order to gain a better predictive understanding of the governing principles associated with this phenomenon, the physical and chemical properties of kaolinite were investigated using an efficient, firstprinciples scheme for studying isomorphic substitution of Al ions in kaolinite by two kinds of other elements (namely, the dual defect). Elements that are relatively common in natural kaolinite were chosen from groups II (Be, Mg, Ca, and Sr) and III (Fe and Sc) of the Periodic Table as dual-defect ions to substitute for Al ions in kaolinite. By systematically calculating the impurity-formation energies (which characterize the difference in the total crystal energy before and after the defect arises) and transitionenergy levels, which characterize the energy cost for the transformation between two different charge states, the (Be + Sc)Al (i.e. the replacement of two specific Al ions in kaolinite by external Be and Sc ions), (Ca + Sc)Al, (Mg + Sc)Al, and (Sr + Sc)Al ion pairs were determined to have low formation energies, suggesting that these combinations of ions can easily substitute for Al ions in kaolinite. The (Be + Fe)Al, (Ca + Fe)Al, (Mg + Fe)Al, and (Sr + Fe)Al ion pairs have relatively high formation energies which make isomorphic substitution (or doping) in kaolinite difficult. Moreover, these combinations of elements from groups II and III were found to have relatively low transition-energy levels compared with other element pairs. Among them, (Sr + Sc)Al have the lowest transition-energy level at 0.06 eV above the valence band maximum. When compared with single external substitutional defects in kaolinite, remarkably, the dual defects have relatively low formation energies and transition-energy levels. The results are helpful in understanding the chemical and physical properties of natural kaolinite.

Few studies have explored the change in thermal stability of poly(oxypropylene) (POP) ammonium ions after intercalation, even though several studies have focused on the modification of montmorillonite (Mt) with POP amine hydrochloride. The purpose of the present study was to understand the effect of chain length of POP amine hydrochlorides on the basal spacing of modified Mt, and the amount and thermal stability of the ammonium ions intercalated. The relations between basal spacing, organic fraction, and thermal stability of the ammonium ions intercalated were also explored. Series of modified Mt were prepared via ion-exchange between Na+-montmorillonite (Na+-Mt) and POP diammonium ions or POP triammonium ions with different chain lengths, and were then characterized by Fourier-transform infrared spectroscopy, X-ray diffraction, and simultaneous differential scanning calorimetry-thermogravimetric analysis. The results revealed that the basal spacing of modified Mt increased with the hydrophobic chain length of the POP ammonium ions. The amount of triammonium ions intercalated was close to the theoretical amount, while the organic fraction of modified Mt was directly proportionalto the basalspacing of modified Mt. The intercalated ammonium ions were, therefore, contained within the interlayer space ofMt. After intercalation, the thermal stability of the POP ammonium ions with various chain lengths was reduced; i.e.Tonset was reduced by 7–60°C for short-chain POP ammonium ions (D400 and T403) and by 177–192°C for long-chain ions (D2000, D4000, T3000, and T5000).

Bentonites are considered suitable backfill material for planned underground nuclear-waste repositories because of an inherent capacity to self-seal and retain contaminants when hydrated. Barrier effectiveness, however, depends on the physical properties of bentonite after placement in a repository site, where hydration state and bulk density can vary. The objective of the present study was to investigate commercial bentonite MX80 hydration rates and mechanisms during water infiltration into dry, moist, and wet samples using the ‘wet-cell’ X-ray diffraction technique. During experimentation, water enters a small flow-through cell and induces swelling within a confined reaction volume, analogous to clay barriers in excavated underground sites. Results demonstrated the importance of using dry, well compacted (>1.4 g/cm3) bentonite, which became saturated slowly (<2.0 ×10−9 m/s) with minimal water in noninterlayer sites (external-surface sites, or within pores). The significant degree of interlayer expansion dominated by the formation of two and eventually three water layers developed as hydration clusters with greater probabilities for the same thickness to lie in adjacent interlayer sites. The relatively thicker particles and the less accessible surface area of hydrated, initially dry bentonite probably resulted in less pore-controlled diffusion, but also less potential radionuclide adsorption by surface complexation. Moist MX80 had the greatest water uptake, the smallest (1.23 g/cm3) dry bulk density, and the greatest proportion of water in pores and on external surfaces. Water that initially accumulated in pore spaces subsequently acted as a reservoir for interlayer hydration and probable gel formation in trapped voids, which is expected to occur in more loosely filled gaps within an excavated repository.

A number of different types of bentonite deposits formed by hydrothermal alteration and diagenetic processes are to be found in the Ordu area of the Eastern Black Sea region. The Ca- and Na-bentonite deposits are related to Upper Cretaceous tholeitic to calc-alkaline volcanites, predominantly dacite and andesite, and also include rhyodacite with lesser basalt and their pyroclastic equivalents. In the present study, dacite (PR1), perlite (PR2), moderately altered rocks (MPR), and Na- and Ca-bentonites were studied to describe and compare their mineralogical and geochemical properties and their conditions of formation by means of X-ray diffraction, optical microscopy, scanning electron microscopy, and chemical analytical techniques.

Ca-bentonites, except for smectite, contain opal-CT, feldspar, biotite, and rarely pyrite, while Na-bentonites contain smectite and less feldspar, opal-CT, kaolinite, and illite.

Progressive alteration of the PR2 caused depletion in K2O and Na2O and enrichment in MgO and CaO in all of the Ca-bentonite samples. Na2O was depleted in all of the Na-bentonites and in most of the MPR. The medium and heavy rare earth elements (MREE and HREE) show mass gain or mass loss in the Na-bentonites. The HREE show nearly immobile behavior in the Ca-bentonites. The rare earth elements (REE) and transition elements (TRE) mostly gained mass in the Ca-bentonites in contrast to Na-bentonites. Large-ion lithophile elements (LILE) are strongly depleted in all of the bentonites. The LREE, MREE, and HREE were strongly depleted in most of the MPR samples. TiO2, Lu, Tm, and Tb show immobile behavior in all samples.

PR1 exhibits a slightly positive Eu anomaly. Two MPR samples show slightly positive Eu anomalies (1.03, 1.13), and one Na-bentonite sample displays a slightly positive Eu anomaly (1.04). Most of the Nabentonites have weakly negative Eu anomalies, whereas perlite and the Ca-bentonite have a strongly negative Eu anomaly. The PR1, PR2, MPR, and Na-bentonite present a positive Ce anomaly, and the Ca-bentonite shows a moderately negative Ce anomaly. The Ca-montmorillonites are mainly hydrothermal in origin and derived from alteration of volcanoclastic material in situ and/or in the subaerial environment. The Na-montmorillonites formed by alteration and diagenesis of volcanoclastic material in the sedimentary basin.

Landfill leachate is one of the most difficult effluents with which to deal from an environmental perspective because of its concentration and complex composition, including refractory and toxic components such as heavy metals or xenobiotic organic compounds. The objective of the present study was to use organically modified bentonite (OMB) to dispose of landfill leachate >10 y old. The OMB was synthesized using a new method, which removed four steps (filtering, washing, drying, and grinding) from the traditional process. After treatment using OMB, the chemical oxygen demand concentration (COD concentration, an index of the organic pollutants in the landfill leachate, was determined using the potassium dichromate method) of the landfill leachate sample decreased from 2400 to 245 mg/L in 5 h, i.e. the organic pollutants reduction efficiency was as high as 90%. Gas chromatography-mass spectrometry results indicated that most of the organic compounds were removed during the process. The modified and unmodified bentonite contained in the OMB deal with the hydrophobic and hydrophilic organic pollutants, respectively, resulting in significant degradation of the leachate. The study results have provided a new cost-effective method for treatment of landfill leachate.

Hydrothermal syntheses of a silicate structure comprising a single tetrahedral layer, known as ilerite, were conducted in the presence of tin (SnCl4·5H2O) as a heteroatom. The main aim of the study was to investigate the influence of the above-mentioned compound on the resulting material, as well as the possibility of isomorphous replacement of Si by Sn atoms. For comparison, unmodified ilerite, ilerite impregnated by SnO2, and ilerite synthesized in the presence of Al (aluminum isopropoxide) were also used. The ilerite structure observed was that of Na-ilerite. Syntheses of samples with various Sn/Si ratios (up to the value of 0.01Sn/4Si) and Al/Si ratios (up to the value of 0.005Al/4Si) resulted in a magadiite structure. Synthesis methods applied to Sn-modified materials were found to be unsuitable for the introduction of tetrahedrally substituted Al. The characterization methods used were X-ray diffraction (XRD), temperature-programmed reduction (TPR), and diffuse reflectance infrared fourier transform (DRIFT) spectroscopy. and these indicated the presence of metal oxide species on the surfaces of the crystals, in addition to a small degree of replacement of Si by Sn or Al in the tetrahedral layers.

The role of Mn oxide in the abiotic formation of humic substances has been well demonstrated. However, information on the effect of crystal structure and surface-chemical characteristics of Mn oxide on this process is limited. In the present study, hexagonal and triclinic birnessites, synthesized in acidic and alkali media, were used to study the influence of the crystal-structure properties of birnessites on the oxidative polymerization of hydroquinone and to elucidate the catalytic mechanism of birnessites in the abiotic formation of humic-like polymers in hydroquinone-birnessite systems. The intermediate and final products formed in solution and solid-residue phases were identified by UV/Visible spectroscopy, atomic absorption spectrometry, Fourier-transform infrared spectroscopy, X-ray diffraction, solid-phase microextraction-gaschromatography-mas ss pectrometry, ion chromatography, and ultrafiltration. The degree of oxidative polymerization of hydroquinone wasenhanced with increase in the interlayer hydrated H+, the average oxidation state (AOS), and the specific surface area of birnessites. The nature of the functional groups of the humic-like polymers formed was, however, almost identical when hydroquinone was catalyzed by hexagonal and triclinic birnessites with similar AOS of Mn. The results indicated that crystal structure and surface-chemistry characteristics have significant influence on the oxidative activity of birnessites and the degree of polymerization of hydroquinone, but have little effect on the abiotic formation mechanism of humic-like polymers. The proposed oxidative polymerization pathway for hydroquinone isthat, asit approachesthe birnessite, it formsp recursor surface complexes. Asa strong oxidant, birnessite accepts an electron from hydroquinone, which is oxidized to 1,4-benzoquinone. The coupling, cleavage, polymerization, and decarboxylation reactionsaccompany the generation of 1,4-benzoquinone, lead to the release of CO2 and carboxylic acid fragments, the generation of rhodochrosite, and the ultimate formation of humic-like polymers. These findings are of fundamental significance in understanding the catalytic role of birnessite and the mechanism for the abiotic formation of humic substances in nature.

Mineral-microbe interactions are widespread in a number of environmental processes such as mineral weathering, decomposition, and transformation. Both clay minerals and silicate-weathering bacteria are widely distributed in nature, and the latter contribute to weathering, diagenesis, and mineralization of major rock-forming minerals. The purpose of this study was to observe changes in the chemical composition and structure, especially the phase transformation, of smectite after processing by a silicate-weathering bacterium. The interaction between Bacillus mucilaginosus and bentonite was studied using custom culture media. Results from Inductively Coupled Plasma-Atomic Emission Spectrometry revealed that the bacterium promoted release of Si and Al from solid bentonite to solution. Concomitantly, the Ka nd Fe contents of the mineral increased as shown by X-ray photoelectron spectroscopy results. After interaction with the bacterium, the montmorillonite underwent a possible structure transformation to smectite, as indicated by the emergence of a new weak peak (d = 9.08 Å) shown by X-ray diffraction patterns. The mineralogical changes were also demonstrated by the decrease in the specific surface area of the mineral from 33.0 to 24.0 m2/g (these lower values for SSA of bentonite are related to the particle size of the smectite examined (120-160 mesh) and the weakened absorption bands in Al-O-H and Si-O-Si vibrations by Micro Fourier-transform infrared spectroscopy. The morphology changes in the bacteria observed by environmental scanning electron microscopy and atomic force microscopy revealed an obvious growth of the flagella in the presence of bentonite.