The term ‘montmorillonite’ encompasses a wide range of chemical compositions and structures. Comprehensive and reliable characterization is essential for unambiguous classification. Twenty eight purified, Na-exchanged smectites (<0.2 µm) were characterized by layer-charge measurement using the alkylammonium method, by cation exchange capacity (CEC) measurement with Cu-triethylenetetramine, by determination of the chemical composition using X-ray fluorescence analysis, by calculation of the structural formula following determination of the octahedral structure (trans-vacant vs. cis-vacant) by simultaneous thermal analysis, and by X-ray diffraction analysis. Mössbauer spectroscopy was applied to determine the oxidation state and coordination of Fe and changes thereof during purification of the source materials.

The charge derived from chemical composition was considerably greater (by up to 30%) than the measured layer charge. The independently measured layer charge was used to calculate the structural formula. The measured CEC values, comprising the permanent charges and the pH-dependent edge charges, were consistent with measured layer charge but not with layer charge derived from the chemical composition. Therefore, the structural formula of smectites should be calculated using the measured layer charge.

The dehydroxylation temperature, which conveys information about the structure of the octahedral sheet, was correlated to the amount of Mg and Fe3+ and the location of charges. No relationship was found among the dehydroxylation temperature and the mean layer charge or the Mg content. In contrast, a clear relationship was observed between the Fe content and the dehydroxylation temperature. Montmorillonites with an Fe content <0.3/f.u. are cis-vacant and those containing Fe3+ > 0.3 mol/f.u. are trans-vacant, mostly with additional cis-vacancies. Tetrahedral substitution also appeared to be a function of the number of trans-vacancies.

The parameters analyzed provide the basis for a new descriptive classification system.

Control of the structure and morphology of clay crystals presents a challenge in the synthesis of materials for adsorption and catalysis. In the present study, direct crystallization of a phyllosilicate grafted with organosilyl (methylsilyl and phenylsilyl) groups on the surface of monodisperse spherical silica particles (2.6 μm) is reported. Methyl- and phenyltriethoxysilanes were allowed to react hydrothermally in a Teflon-lined autoclave with silica, MgCl2, and LiF in the presence of urea for 2 or 4 days. X-ray diffraction patterns revealed that the fine platy particles formed were a trioctahedral hectorite-like layered silicate. Greater temperature (150°C) was required to achieve homogeneous coverage of the original spherical silica particles with the hectorite-like particles. The diameter of the initial silica grains increased slightly to 3.0 μm after the hydrothermal reactions, while the original spherical shape and size distribution were maintained. Solid-state 29Si nuclear magnetic resonance analyses confirmed that the presence of resonances attributed to the RSi(OMg)(OSi)2 and RSi(OMg)(OH)(OSi) (R = methyl or phenyl) environments of the silicon proved the formation of covalent bonds between phyllosilicate sheets and the organic moieties. The crystallinity of the layered silicates increased when the reactions ran for a longer time (4 days).

Due to the environmental problems derived from the use of common surfactants as modifiers for clay mineral adsorbents to mitigate mycotoxin contamination of animal feeds, finding non-toxic modifiers to prepare safe and efficient adsorbents is necessary. The objective of the present study was, therefore, to modify acidified palygorskite with polyhexamethylene biguanide (PHMB) to obtain antibacterial polyhexamethylene biguanide/palygorskite (PHMB/Plg) composites for the removal of zearalenone, a common mycotoxin. The PHMB/Plg composites were characterized and analyzed by X-ray diffraction, Fourier-transform infrared spectroscopy, field-emission scanning electron microscopy, and isothermal nitrogen adsorption analysis. The adsorption properties of the composites with respect to zearalenone and their antibacterial activity with respect to Escherichia coli and Staphylococcus aureus were studied. The results indicated that the hydrophobicity of palygorskite was enhanced after modification with PHMB, which could effectively improve the adsorption property of palygorskite toward the nonpolar zearalenone molecules. The adsorption capacity of PHMB/Plg increased with increasing amounts of polyhexamethylene biguanide and increasing pH. The adsorption data were described well by pseudo-second order kinetics and by the Langmuir adsorption model. The maximum adsorption capacity was 2777 μg/g. When the amount of PHMB added increased to 15 wt.%, the composites obtained exhibited good antibacterial performance, and the minimum inhibitory concentrations for Escherichia coli and Staphylococcus aureus were both at 2.5 mg/mL.

The influence of epigenetic (pre-pedogenetic) alteration of basic and ultrabasic rocks leading to the formation of phyllosilicate mineral associations is not well known. The purpose of this study was to gain further understanding of the processes involved by investigating the mineral associations of shallow soils underlain by amphibolites and metamorphosed gabbro-diabases (East Fennoscandia) and by serpentinous dunites (olivinite) and metagabbro amphibolites (the Ural Mountains). Where phyllosilicates were absent from the bedrock, they were also absent from the sola. The pedogenic alteration of the initial mineral soil matrix was very weak and did not result in a significant accumulation of phyllosilicates in the soils (East Fennoscandia). Pedogenesis enhanced the transformation of phyllosilicates, a process initiated by epigenic rock alteration.

Phyllosilicates in the sola from basic and ultrabasic rocks of the Polar Urals were largely inherited according to their origin. The inherited phyllosilicate association of the sola from ultrabasic rocks included talc, serpentine, and chlorite. Saponite resulted from pedogenesis; its distribution in various thin soils dependingon the processes of neoformation and decomposition, the latter probably taking place under the influence of lichens and moss.

Chlorite and illite and products of their transformation, including vermiculite, comprise the phyllosilicate association of a solum from basic rock, and traces of talc were found. The distribution of vermiculite and randomly interstratified chlorite-vermiculite (C-V) depended on the processes of chlorite vermiculitization and vermiculite decomposition.

The formation conditions of the ferric smectite nontronite are not fully understood. The present study couples experimental and analytical data with field observations in an attempt to constrain the rate and temperature of formation of naturally occurring nontronites from Columbia River Basalt flows. Synthetic Fe-Al-Si gels were incubated at temperatures ranging from 4 to 150°C for 4 weeks. Samples were analyzed using Fe K-edge X-ray fluorescence spectroscopy (XAFS). Spectra of the synthesized nontronites were compared with spectra of natural samples collected from weathered Columbia River Basalt flows. Cation ordering in the synthetic samples increased with incubation temperature, but the synthetic clays did not approach the degree of crystal ordering of the natural nontronite samples. These observations suggest that highly ordered natural nontronites require longer crystallization times than are typically used in laboratory experiments. The natural samples were found filling open cracks near flow surfaces, indicating that the clays formed at temperatures below the boiling point of water. A comparison of experimental and field timescales with other estimates of nontronite growth rates suggests that natural nontronite crystallization in the region must have occurred at ambient, near-surface temperatures over timescales of up to millions of years.

The electron back-scattered diffraction (EBSD) technique has been applied to fine-grained kaolin minerals to determine the polytypes (kaolinite, dickite and nacrite) of individual grains and their crystallographic orientations in a scanning electron microscope (SEM). Because kaolin minerals are prone to radiation damage by the intense electron beam necessary to obtain EBSD patterns, the beam has to be rastered across the specimens during pattern acquisition. Kaolinite-dickite and nacrite are easily distinguished by their trigonal or hexagonal symmetry about the [001]* direction, respectively, of the Kikuchi bands with k = 3n. Dickite can be differentiated from kaolinite by mirror symmetry parallel to the a-c plane, and by the characteristic contrast of HOLZ rings.

As EBSD analysis is performed using a SEM, morphological characters can be correlated with polytypes. Dickite fragments could be discerned as oriented overgrowths on nacrite plates. Dickite was observed to always adopt euhedral shapes in a diagenetic mixture of kaolinite and dickite. Lath-shaped dickite is elongated along the a axis direction. Rhombohedral dickite consists of crystals with {1̄11} indexed to the side facets.

The Maramures Basin, in the Carpathian mountain belt of northern Romania on the border with the Ukraine, belongs to the eastern part of the Pannonian Basin. In the study area, extensional tectonic movements during the Miocene were coeval with silicic and intermediate volcanism in the inner part of the Eastern Carpathians. Throughout this region, explosive events have resulted in the deposition of pyroclastic flows and ash-fall deposits interbedded with marine sediments.

Several tuff units of Badenian (15–13.6 Ma) age occurring throughout the area are extensively zeolitized. These rocks occur as massive homogeneous beds, white to pale greenish-blue, and are commonly extensively jointed. In the Bârsana-Calinesti area and along the Morii Valley, two conspicuous tuff units that can be traced over many km are separated by a calcareous sandstone bed. Most tuffs have a vitroclastic texture in which former glass shards are pseudomorphed by clay minerals and clinoptilolite. Opal-CT commonly occurs as clumps of radiating rods that produce a spherical morphology. Also, rare celadonite is found in the lower greenish tuffs. Pyrogenic crystal fragments are quartz, plagioclase and biotite. Folded muscovite plates and fragments of basement rocks are dominant among the lithic clasts. Above the Bârsana Formation, a second series of white zeolitized tuff, the Ocna Sugatag Formation, is represented by at least two different units overlying an evaporite salt deposit. A large outcrop of a massive white tuff at this locality contains abundant fine-grained clinoptilolite and cation-exchange capacity values of >160 meq/100 g. Clinoptilolite-Ca is also present in the Sighetu tuff unit in the northern part of the Maramures Basin where a distinctive horizon contains plant remains preserved in spherical concretions. Plant material and algal limestones in the same succession strongly suggest that the marine depositional environment was close inshore, and shallow-rather than deep-water conditions are inferred. A mineralogically similar, unaltered, volcanic tuff found in the Coas area suggests that the precursor glass was rhyolitic (72–74% SiO2) with a high-K calc-alkaline affinity. We conclude that pervasive zeolitization is due to the interaction between seawater and vitroclasts at an early stage after deposition.

In spite of many studies of kaolinite synthesis, questions remain as to the transformation of gel into kaolinite, the kinetics of the reaction, and the influence of solution chemistry. The purpose of the present study was to perform a hydrothermal synthesis in order to understand better the transformation from boehmite to kaolinite. Kaolinite was synthesized from amorphous SiO2 and Al(OH)3·xH2O at fixed temperature (250°C) and pressure (30 bar). The initial pH of the solution was 2. The reaction time for the synthesis was varied from 2 to 36 h. The physical properties of synthesized kaolinite were characterized by X-ray diffraction (XRD), infrared spectroscopy (IR), nuclear magnetic resonance (NMR) spectroscopy, field-emission-scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM), and energy dispersive spectrometry (EDS).

The early stage of kaolinite synthesis followed activation of amorphous Al(OH)3·xH2O to initiate the reactions, i.e. ionization and subsequent crystallization of boehmite. The boehmite reacted continuously with Si4+ dissolved in solution and gradually transformed to disordered, lath-shaped boehmite. In XRD and IR patterns, the typical peaks of boehmite were weakened or disappeared following the reaction.

Structural transformation from boehmite to kaolinite occurred when the Al/Si ratio of the aluminosilicate was 1.0. The kaolinite formed was in the form of curved flakes and its crystallinity increased with reaction time. In the final stage of reaction the morphology of kaolinite changed from flaky to polygonal. The hexagonal, platy kaolinite was therefore developed to allow the gradual variation of the chemical composition, crystal structure, and morphology.

Ion adsorption-type rare earth deposits (IADs) are developed via prolonged weathering of REE-rich volcanic and metamorphic rocks. Intense magmatic activity which occurred during the Yanshanian (199.6–65.5 Ma) and Caledonian periods (542–359.2 Ma) provided an abundant material basis for the formation of IADs in South China. High concentrations of REE and the high proportion of ion-exchangeable REE were found in the Maofeng Mountain regolith, Guangzhou city. However, the geochemical patterns and mechanisms of REE enrichment in the regolith were still poorly understood. The present study investigated the regolith profile (0–8 m) developed in Maofeng Mountain based on metallogenic and geochemical characteristics, sequential extraction, and physical and chemical parameters of the regolith profile. The bedrock contained abundant REE resources (245–287 mg kg–1) and the chondrite-normalized REE patterns showed the enrichment of light REE (LREE) and negative cerium (Ce) and europium (Eu) anomalies. The distribution patterns of REE in the bedrock were inherited by the regolith. REE enrichment of the regolith occurred mainly in the completely weathered layer (B1, B2, and B3 horizons), particularly in the depth range 2.5–4.5 m (849–2391 mg kg–1). The position of REE enrichment was controlled by the soil pH (5.52–6.02), by the amount of kaolinite and halloysite, and by the permeability of the metamorphic rock. In the REE-enriched horizon (2–8 m), the REE were hosted mainly in ion-exchangeable fractions (75–2158 mg kg–1), representing 79% of the total REE. Given the pH of 4.73–6.02, REE fractionation driven by the adsorption of kaolinite was limited. Fe–Mn (oxyhydr)oxides played an important role in REE enrichment and the reducible fraction holds up to 21% (139 mg kg–1) of the total REE. The enrichment of LREE was observed in the reducible fraction potentially because of the preferential release of LREE from the LREE-bearing minerals (monazite) and then scavenged by Fe–Mn (oxyhydr)oxides. Positive Ce anomalies (Ce/Ce*: 10) were found in the reducible fraction because trivalent Ce was oxidized by Fe–Mn (oxyhydr)oxides to cerianite (CeO2). The present study helps to understand the enrichment and fractionation of REE in the IADs of South China.

The organization of organic species on the ordered structures of clays and clay minerals is one way to produce inorganic-organic hybrids with controlled microstructures and properties. The reactions of the adsorbed species and their arrangement on the clay surfaces can be guided by the choice of clay and of adsorbed species. The purpose of the present study was to intercalate alkylammonium ions into a Thai bentonite and to study the effect on dye-adsorption efficiency. A series of alkylammonium ions, CnH2n+1NH3+ (n = 8, 10, 12, or 18), was incorporated into the interlayer spaces of a natural bentonite by mixing an aqueous dispersion of bentonite with an aqueous solution of protonated alkylamines at room temperature. The basal spacings of the intercalation compounds varied depending on the alkyl chain lengths and the amount of alkylammonium ions. The alkylammonium ions adsorbed formed lateral monolayer, bilayer, pseudo-trimolecular layer, paraffin-type monolayer, and/or paraffin-type bilayer structures. The adsorption efficiency of alkylammonium-bentonites was determined using batch adsorption experiments of rhodamine 6G from a water-ethanol solution; the greatest efficiency was 87% while that of the bare bentonite was 47%. The loading amount and the arrangement of the intercalated alkylammonium ions in the interlayer spaces, as well as the specific surface area and pore volume, played important roles in the adsorption efficiency of alkylammonium-bentonite. The adsorption equilibrium data for rhodamine 6G on the best adsorbent were interpreted using the Langmuir isotherm model and a pseudo-second order kinetics model. The adsorption efficiency of the adsorbent decreased by only 17% after five runs.

Allophane is a very fine-grained clay mineral which is especially common in Andosols. Its importance in soils derives from its large reactive surface area. Owing to its short-range order, allophane cannot be quantified by powder X-ray diffraction (XRD) directly. It is commonly dissolved from the soil by applying extraction methods. In the present study the standard extraction method (oxalate) was judged to be unsuitable for the quantification of allophane in a soil/clay deposit from Ecuador, probably because of the large allophane content (>60 wt.%). This standard extraction method systematically underestimated the allophane content but the weakness was less pronounced in samples with small allophane contents. In the case of allophane-rich materials, the Rietveld XRD technique, using an internal standard to determine the sum of X-ray amorphous phases, is recommended if appropriate structural models are available for the other phases present in the sample. The allophane (+imogolite) content is measured by subtracting the amount of oxalate-soluble phases (e.g. ferrihydrite). No correction would be required if oxalate-soluble Fe were incorporated in the allophane structure. The present study, however, provides no evidence for this hypothesis. Mössbauer and scanning electron microscopy investigations indicate that goethite and poorly ordered hematite are the dominant Fe minerals and occur as very fine grains (or coatings) being dispersed in the cloud-like allophane aggregates.

Allophane is known to adsorb appreciable amounts of water, depending on ambient conditions. The mass fraction of the sample attributed to this mineral thus changes accordingly; the choice of a reference hydration state is, therefore, a fundamental factor in the quantification of allophane in a sample. Results from the present study revealed that (1) drying at 105ºC produced a suitable reference state, and (2) water adsorption has no effect on quantification by XRD analysis.

The conformational behavior of polymers in clay-polymer nanocomposites (CPN) is not fully understood because of the many factors involved. The purpose of the present study was to investigate the conformational behavior of a polymer at the micro- and meso-scales in order to predict the behavior of tunable CPN. The study used a pH-responsive polymer, polyacrylamide, which has time-dependent hydrolysis response properties, to examine micro-scale conformational behavior of the polymer adsorbed on representative clay-mineral surfaces, SiO2 and Al2O3. A nanocomposite and a microcomposite were used to link meso-scale CPN behavior to micro-scale polymer conformation. The conformational behavior was characterized using in situ, real-time spectroscopic ellipsometry. The contracted coil conformation of polyacrylamide was observed at pH = 3, while extended conformation was observed at pH = 11.5 on both SiO2 and Al2O3 surfaces. At pH = 11.5, the polymer conformation changed from expanded coil to extended conformation over time. The polymer conformation changed more rapidly with the Al2O3 surface due to mineral dissolution at pH = 3 and 11.5. Swelling tests were conducted as functions of pH and time to link the micro-scale phenomena to meso-scale CPN behavior. The results indicated that the swelling potential of CPN corresponded to the conformation of adsorbed polyacrylamide, which varied with pH and time. The swelling potential of CPN was maximized at pH = 11.5 and decreased with decreasing pH, corresponding to the observed micro-scale conformational behavior.

Unconformity-related uranium deposits, which represent a significant high-grade uranium resource, are systematically surrounded by a host-rock alteration halo enriched in clay minerals. Illite is often the major clay mineral component of the halo and it displays a variable crystal structure. New data are provided on the crystal structure and the chemistry of illite encountered within and outside of the alteration halo surrounding the Shea Creek deposit. Two illite populations were distinguished using textural and structural criteria: samples rich in the tv-1M polytype display thin (sub-micrometer) and ‘hairy’ shapes, while samples richer in the cv-1M polytype contain illites with rigid lath-like shapes several micrometers wide. In barren ‘regional’ sandstone, the trends with depth of the textural and microstructural properties of illite particles are: (1) an increase of particle size, (2) an evolution to a more isometric form, and (3) a dominance of the cv-1M polytype over the tv-1M polytype. These trends record diagenetic processes under conditions of deep burial and differ from those observed in altered sandstone around the uranium mineralization. The altered sandstone is characterized by enrichment in the tv-1M polytype near the unconformity and/or brittle structural features. This tv-1M illitization took place in response to structurally-controlled infiltration of basement rocks by diagenetic brines which were further recycled after interaction into the overlying basin. Variations of the illite structural and textural properties may result from nucleation/growth kinetics and may be indicative of a change in the flow regime, and/or a change of saturation state of the fluid vs. illite. The tv-1M illite may be favored in environments characterized by a high fluid/rock ratio and a high supersaturation state of the fluids in proximity to mineralization.