The Al-clay-rich rock units at Mawrth Vallis, Mars, have been identified as mixtures of multiple components based on their spectral reflectance properties and the known spectral character of pure clay minerals. In particular, the spectral characteristics associated with the ~2.2 μm feature in Martian reflectance spectra indicate that mixtures of AlOH- and SiOH-bearing minerals are present. The present study investigated the spectral reflectance properties of the following binary mixtures to aid in the interpretation of remotely acquired reflectance spectra of rocks at Mawrth Vallis: kaolinite-opal-A, kaolinite-montmorillonite, montmorillonite-obsidian, montmorillonite-hydrated silica (opal), and glass-illite-smectite (where glass was hydrothermally altered to mixed-layer illite-smectite). The best spectral matches with Martian data from the present study’s laboratory experiments are mixtures of montmorillonite and obsidian having ~50% montmorillonite or mixtures of kaolinite and montmorillonite with ~30% kaolinite. For both of these mixtures the maximum inflection point on the long wavelength side of the 2.21 μm absorption feature is shifted to longer wavelengths, and in the case of the kaolinite-montmorillonite mixtures the 2.17 μm absorption found in kaolinite is of similar relative magnitude to that feature as observed in CRISM (Compact Reconnaissance Imaging Spectrometer for Mars) data. The reflectance spectra of clay mixed with opal and of hydrothermally altered glass-illite-smectite did not represent the Martian spectra observed in this region as well. A spectral comparison of linear vs. intimate mixtures of kaolinite and montmorillonite indicated that for these sieved samples, the intimate mixtures are very similar to the linear mixtures with the exception of the altered glass-illite-smectite samples. However, the 2.17 μm kaolinite absorption is stronger in the intimate mixtures than in the equivalent linear mixture. Modified Gaussian Modeling of absorption features observed in reflectance spectra of the kaolinite-montmorillonite mixtures indicated a strong correlation between percent kaolinite in the mixture and the ratio of the area of the 2.16 μm band found in kaolinite to the area of the 2.20 μm band found in montmorillonite.

The island of Lipari (Italy) is characterized by calc-alkaline to potassic volcanism and a Mediterranean-type climate. The mineralogical and chemical features of two different soil profiles with ages of 92,000 and 10,000–40,000 y, respectively, have been investigated. There were no Andisols, but Vitric and Vertic Cambisols have developed at both sites. Although the morphology of the soils was similar, remarkable differences in the clay mineralogy between the two sites were observed. The site with the Vitric Cambisol was associated with the weathering sequence: glass → halloysite → kaolinite or interstratified kaolinite-2:1 clay minerals. Both sites had smectite in the clay fraction and, to a large extent, this smectite had a low charge and could be characterized as a dioctahedral montmorillonite. At the site with a Vertic Cambisol, smectite was the predominant mineral phase in the clay fraction. The smectites (predominantly montmorillonite) found in this soil were probably not of pedogenetic origin and are, therefore, inherited from the parent material. Their formation is due to hydrothermal alteration of glass particles during or immediately after the emplacement of the pyroclastic flow. The octahedral character of the smectites did not change from the C to the A horizon indicating that they are resistant to weathering processes. A high-charge expandable mineral was detected in small concentrations in the Vertic Cambisol and had a dioctahedral structure. In this case also, no signs of significant weathering or transformation could be detected in the soil profile. In contrast to many other investigations, no active smectite formation within the soil profiles could be measured. The subtropical and rather dry climate in Lipari might, therefore, favor the persistence of dioctahedral low-charge montmorillonites that are associated with a small amount of a high-charge expandable mineral in the soil.

Giovanni Pico della Mirandola (1463–1494) ha raccolto la sua collezione di libri in tempi e con modalità diverse a seconda degli studi, degli obiettivi e delle fonti disponibili. I due inventari superstiti, entrambi compilati dopo la sua prematura morte avvenuta all’età di 31 anni, rivelano notevoli lacune nel corpus aristotelico. Nonostante ciò, i volumi rimasti e quelli che possiamo ipotizzare che gli sono appartenuti dimostrano che nella sua breve vita egli riuscì a riunire la più grande collezione di opere di Aristotele del suo tempo, con testi in greco, in latino, in ebraico e persino in arabo. Alle versioni medievali aggiunse anche quelle umanistiche.

Numerous studies have investigated the ligand-promoted dissolution of Fe (oxyhydr)oxides. In natural environments, inorganic ligands can compete with organic ligands for surface sites on (oxyhydr)oxides which may influence dissolution rates. Published research of this interaction and its effect on the dissolution of (oxyhydr)oxides is rare. The objective of the present study was to examine the extent to which silica, as a naturally occurring competitive ligand added in the form of silicic acid, impacts the oxalate-promoted dissolution of the common soil Fe (oxyhydr)oxide goethite. Sorbed silica reduced the oxalate-promoted dissolution rate of goethite at all surface coverages investigated. As initial silica solution concentrations increased from 0.50 mM to 5.0 mM, relatively little change in the dissolution rate was observed. Fourier-transform infrared (FTIR) spectra indicated that, as silica-surface coverages increased, the silica underwent polymerization on the goethite surface. Initially, silicate was associated with surface functional groups, but as polymerization occurred some of the silica appeared to desorb from the goethite surface without being released into the bulk solution, suggesting that silica polymers formed discrete islands or surface clusters that grew away from the goethite surface rather than expanding epitaxially across the surface. Minimal changes were observed in the quantity of reactive goethite surface, which is responsible for the observed dissolution rates, as silica-surface coverages increased.

The Hançılı bentonite from Turkey shows significant changes in surface area, micro- and mesoporosity, surface acidity and acid strength with heating from 100 to 900°C for 2 h. The specific surface area (S) and specific micro-mesopore volume (V) of the original and heated samples were evaluated from N2 adsorption and desorption data, respectively, by standard methods. The adsorption of n-butylamine from the solution in cyclohexane on the samples was used to determine the total surface acidity (nm) and the adsorption equilibrium constant (K) was taken as a measure of the acid strength. S, V and nm having initial values of 98 m2g−1, 0.080 cm3g−1 and 4.8 × 10−4 mol g−1, respectively, stayed approximately constant as the temperature increased to 450°C and then decreased almost in parallel with each other, reaching their minimum or zero at 900°C. The total surface acidity, in general, declines with increasing temperature. The most acidic sites, however, increase with heating, and especially at dehydration and dehydroxylation. Acid strength reaches its maximum during the dehydroxylation phase at ∼600°C. It was concluded that the total surface acidity does not necessarily parallel the strength of the most acid sites.

Mesoporous materials have a wide range of applications in the fields of nanotechnology, biotechnology, information technology, and medicine, but historically, the resource materials used for their synthesis have been expensive. Natural silicate minerals are characterized by their abundance, low cost, and large SiO2 contents, making them an alternative silicon source for mesoporous silica. The objective of the present study was to determine the utility of natural chlorite as the source of Si for synthesizing hexagonal mesoporous silica materials (MCM-41). The natural chlorite was pretreated by acid leaching and calcination, followed by a hydrothermal reaction with cetyltrimethylammonium bromide (CTAB) as the template, and subsequent calcination to prepare MCM-41. The structures and the porosity of MCM-41 were characterized by powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), 29Si magic-angle spinning solid-state nuclear magnetic resonance spectroscopy (29Si MAS NMR), and N2 adsorption–desorption measurements. The mechanism of structural evolution from natural chlorite to MCM-41 was investigated using these techniques. Calcination of chlorite results in amorphization and partial structural breakdown, while subsequent acid leaching dissolves the Mg and Al in the octahedral sheets to leave the Si–O framework as a silicon source. 29Si MAS NMR results revealed that the ratio of Q4/Q3 increased from 0.91 to 1.21 after hydrothermal synthesis of MCM-41 from leached chlorite, demonstrating more polymerization of the Si–O structure in MCM-41. The final MCM-41 products were amorphous SiO2, with a large surface area of 630 m2/g, a pore volume of 0.46 mL/g, and a narrow pore-size distribution of 2.8 nm. MCM-41 showed favorable adsorption toward methylene blue (MB) with a monolayer adsorption capacity of up to 302 mg/g, indicating potential for application in adsorption.

Edible clays are consumed by diverse groups of people, especially of African descent, living in Africa and abroad, in a behavior known as geophagy. The clays are used topically as an emollient and drying agent and internally to control diarrhea. Scientific information concerning the chemical constituents and toxicity of edible clays is scarce. The aims of the present study, therefore, were to ascertain the chemical composition of white edible clays (WEC) and gray edible clays (GEC); to determine their toxicity profiles using analytical chemical methods; to test the acute and sub-acute toxicity of edible clays in their natural form as consumed; and to compare the raw and processed clays, and also to compare the latter to a proprietary drug known as ‘Mist kaolin’ (Moko®) which contains some clay along with other chemicals. Atomic absorption spectroscopy (AAS) and gas chromatography/mass spectrometry (GC/MS) were used to determine the elements present. White female Wistar mice and rats were used for the acute and sub-acute toxicity analyses, respectively. The results from AAS showed the presence of heavy metals and metalloids in both GEC and WEC, and the GC/MS revealed the presence of contaminants such as indomethacin and ethyl benzene, but quantities were below human toxicity levels. Doses of 100–500 mg/kg of either clay type could be harmful to the digestive system, but all of the tests revealed that edible clay is not toxic to humans unless very large amounts (500–1000 mg/kg of body weight) are consumed.

Clay is unique especially from the perspective of medical geology, that is, the impacts of geologic materials and geologic processes on animal and human health. Clay is the only natural material that can impact human health through all routes of exposure: ingestion, inhalation, and dermal contact. Moreover, these impacts can be harmful as well as beneficial. Ingestion of clay, a form of geophagy, has been practiced for millennia and is still widely practiced today. Humanoids have been ingesting clay for at least two million years to ease indigestion and counteract poisons. Some additional benefits may accrue from eating clays such as providing some nutrients but these benefits are far outweighed by the likely negative consequences such as tissue abrasion, intestinal blockage, anemia, exposure to pathogens and toxic trace elements, and potassium overdose. Inhalation of airborne minerals including clays has impacted the heath of millions. In the 1930s thousands of people living in the Dust Bowl in the U.S. southwest inhaled copious amounts of clay contributing to deadly ‘dust pneumonia.’ Using clay as a poultice to stem bleeding and cure certain skin ailments is an age-old practice that still has many adherents. A classic recent example of the antibacterial properties of clay is the use of certain clays to cure Buruli ulcer, a flesh eating disease. However, walking barefoot on clays in certain volcanic soils can result in non-filarial podoconiosis or elephantiasis. The absence of clays in soils can have serious health consequences. In South Africa, clay-poor soils yield crops lacking in essential nutrients and may be the principal cause of Msileni joint disease. Clearly, a detailed knowledge of the clays in the environment can have significant benefits to human health and wellbeing.

Modification of the surfaces of montmorillonite (Mnt) by organic molecules is an effective method for improving their affinity toward non-aqueous substances, and has resulted in extensive industrial applications as rheological control agents, drilling fluids, and other functional materials used in applications ranging from environmental remediation to coatings. The present study reviewed recent progress in organo-modification of Mnt, and provides state-of-the-art insights into proposed modification mechanisms and the peculiar functionalities of the resulting organo-montmorillonite (OMnt). Several routes have been employed to modify Mnt, including ion exchange with organic ions, surface adsorption, and grafting of organics. Commonly used organic modifiers include cationic, anionic, zwitterionic, non-ionic, and polymeric species. Organo-modification is driven by multiple interactions: van der Waals forces, cation exchange, electrostatic interaction, hydrogen bonds, and ion–dipole interaction. OMnt, in general, exhibits synergistic and/or antagonistic effects when used in oil-based drilling fluids, environmental remediation, or layered silicate/polymer nanocomposites. The detailed mechanisms of non-ionic and zwitterionic modification of Mnt remain unclear. This literature survey suggests that future work should emphasize deeper understanding of interactions between the Mnt and the organic modifiers, and meanwhile expand the applications of OMnt into catalysis, drug carriers, and the biomedical field.

The source and temporal changes of minerals transported by the world's large rivers are important. In particular, clay minerals are important in evaluating the maturity of suspended sediments, weathering intensity, and source area. To examine seasonal changes in mineralogical compositions of the Changjiang River (CR), suspended particulate matter (SPM) samples were collected monthly for two hydrological cycles in Nanjing city and then were studied using X-ray diffraction (XRD), diffuse reflectance spectrophotometry (DRS), X-ray fluorescence spectrometry (XRF), and chemical analyses. The results indicate that the concentration of CR SPM ranges from 11.3 to 152 mg/L and is highly correlated to the rate of water discharge, with a greater concentration in flood season and lower concentrations during the dry season. CaO, MgO, and Na2O increase with increasing discharge whereas Al2O3 decreases sharply with increasing discharge. Dolomite, calcite, and plagioclase show strikingly similar seasonal variations and increase with increasing discharge with maximum concentrations in the flood season. In contrast, the clay mineral content exhibits the opposite trend with the lowest concentrations in the flood season. Illite dominates the clay minerals of the CR SPM, followed by chlorite, kaolinite, and smectite. Illite and kaolinite show distinctly seasonal variations; SPM contains more illite and less kaolinite during the flood season than during the dry season. The illite chemistry index and crystallinity, as well as kaolinite/illite ratio, all indicate intense physical erosion in the CR basin during the rainy season. Total iron (FeT) and highly reactive iron (FeHR) concentrations display slight seasonal changes with the smallest values observed during the flood season. Goethite is the dominant Fe oxide mineral phase in the CR SPM and hematite is a minor component, as revealed by DRS analyses. The FeT flux and FeHR flux are 2.786×106 T/y and 1.196×106 T/y, respectively.

The thermal stability of bentonite is vitally important for its application in the casting field and the layer charge of montmorillonite (Qm) is one of its central crystal-chemical parameters. As the main component of bentonite, the influence of Qm on montmorillonite properties and behavior needs to be considered if bentonite is to be used in high-temperature environments. The objective of the current study was to investigate the relationship between Qm and the thermal stability of Chinese bentonite samples collected from Wuhu, Anhui Province (marked as WH); Xinyang, Henan Province (marked as XY); and Santai, Sichuan Province (marked as ST) below. The values of Qm were obtained using the O (11) method, and the structural properties of the bentonite samples were characterized by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), thermogravimetry-differential scanning calorimetry (TG-DSC), and field emission scanning electron microscopy (FESEM). The results showed that, in the samples investigated, Qm was inversely related to the thermal stability of bentonite. The Qm value (electrons per half unit cell, e/huc) was greatest for sample ST (0.725 e/huc), followed by sample XY (0.470 e/huc), and by sample WH (0.354 e/huc). The dehydroxylation temperature changed related to Qm; the sample with the largest Qm value was WH (701°C), followed by sample XY (684°C), and sample ST (630°C). After the samples were calcined at 600°C, sample WH had the best montmorillonite structural integrity with the greatest degree of reusability (78.21%); while the montmorillonite structures of samples XY and ST were destroyed, and their reusabilities were only 9.48 and 6.01%, respectively.

The electrical state of the interface between a kaolinite-dominated clay sample and aqueous electrolyte solutions was characterized using low-frequency conductance measurements. From these measurements, the ζ-potential and surface conductivity contributions from the diffuse and non-diffuse parts of the electrical double layer were obtained. The suspensions were studied as a function of volume fraction, electrolyte concentration, and electrolyte type (LiCl, NaCl, KCl, CsCl, CaCl2, SrCl2, and BaCl2). Interpretation in terms of the surface conductance revealed that a substantial part of the surface conductivity originates in the inner part of the double layer. Electrokinetic potentials and related diffuse double layer properties are highly dependent on the nature of monovalent counterions, whereas divalent counterions do not show such clear dependencies. Further presented was a simple way to estimate the order of magnitude of counterion mobilities in the inner part of the electrical double layer. All counterions were shown to have a substantial mobility in the inner part of the double layer. Finally, we suggest that the apparent ion-specific effects observed in the diffuse part of the double layer are at least in part related to the finite size of the counterions. Our findings are relevant to scenarios where fluid flow in porous media is accompanied by charged species transport, e.g., in electro-osmotic remediation, spectral-induced polarization, or permeability measurements.

Sudoites exhibit different crystal-chemical and textural properties which may be related to the structural and valence state of Fe. Mössbauer spectroscopic analysis shows that all Fe previously analyzed using a microprobe (from 1 wt.% to 7.2 wt.% total Fe as Fe2O3) is structural and occurs in both oxidation states (40% Fe2+ and ∼60% Fe3+). Electron microprobe analyses from ∼200 sudoites indicate that Fe occurs in both octahedral sheets according to three main types of substitution: Fe3+ = octahedral Al; Fe2+ = Mg; and Fe3+ + Fe2++ □ = 3Mg. Decreasing tetrahedral substitution balances Fe3+ substitution in the trioctahedral sheet. Increasing octahedral Fe results in a more dioctahedral character of sudoite.

X-ray diffraction (XRD), Fourier transform infrared (FTIR) spectroscopy, differential thermal analysis (DTA) and scanning electron microscope-transmission electron microscope (SEM-TEM) analyses showed that increasing octahedral Fe is associated with decreased stacking order and thermal stability due to the greater number of defects. In addition, with increasing octahedral Fe in sudoite, particles became smaller and more anhedral and consequently less stable with increasing Fe content. These structural and textural variations are interpreted as a result of the distortion of the sudoite structure by substitutions of Fe3+ with larger ionic radii for Al and Mg octahedral cations and by the formation of octahedral vacancies.

Ion-exchange modeling is one of the most widely used methods to predict ion adsorption data on clay minerals. The model parameters (e.g. number of adsorption sites and the cation adsorption capacity of each site) are optimized normally by curve fitting experimental data, which does not definitively identify the local environment of the adsorption sites. A new approach for constructing an ion-exchange model was pursued, whereby some of the parameters needed were obtained independently, resulting in fewer parameters being based on data-curve fitting. Specifically, a reversed modeling approach was taken in which the number of types of sites used by the model was based on a previous first-principles Density Functional Theory study, and the relative distribution of these sites was based on the clay’s chemical composition. To simplify the ion-exchange reactions involved, montmorillonite was Na-saturated to produce a well-controlled Na-montmorillonite (NaMnt) adsorbent. Ion adsorption data on NaMnt were collected from batch experiments over a wide range of pH, Cs+ concentrations, and in the presence of coexisting cations. Ion-exchange models were developed and optimized to predict these cation adsorption data on NaMnt. The maximum amount of adsorption of monovalent cations on NaMnt was obtained from the plateau of the adsorption envelope data at high pH. The remaining equilibrium constants (pK) were optimized by curve fitting the edges of the adsorption envelope data. The resultant three-site ion-exchange model was able to predict the retention of Li+, Na+, K+, and Cs+ very well as a function of pH. The model was then tested on adsorption envelopes of various combinations of these cations, and on Cs+ adsorption isotherms at three different pH values. The pK values were constant for all assays. The interlayer spacing of NaMnt was also analyzed to investigate its relation with cation adsorption strength. An X-ray diffraction study of the samples showed that the measured d001 values for these cations were consistent with their adsorption pK values. The Cs+ cation showed a strong ability to collapse the interlayer region of montmorillonite. In the presence of multiple competing cations, the broadening and presence of multiple d001 XRD peaks suggested that the cations in the interlayers may be segregated.

Todorokite is a common Mn oxide mineral in terrestrial and ocean-floor environments, and it is commonly synthesized from layered Na-buserite. Pyrophosphate, which is known to form strong complexes with Mn(III) at a pH range of 1–8, was added to a suspension of Na-buserite in order to sequester the available Mn(III) in Na-buserite. No Mn(III)-pyrophosphate complex was formed in solution at pH 10, and the treated Na-buserites were converted completely to todorokite. Significant transformation reductions were observed when Na-buserite was treated with pyrophosphate solution at pH 7. The presence of Mn(III) within the MnO6 octahedral sheets of Na-buserite is critical for the transformation from layered buserite to tunnel-structured todorokite at atmospheric pressure. At lower pH, two effects are combined to reduce the amount of Mn(III) in the layers: (1) the complexing power of pyrophosphate is increased; and (2) the transformation from Na-buserite to H-birnessite, which is concomitant with the migration of Mn(III) from layers to the interlayer, and the partial disproportionation of Mn(III). The results showed that Mn(III) played a key role in the transformation of layered Na-buserite to tunnel-structured todorokite at atmospheric pressure.

Structure control and quantitative evaluation of porous materials are essential for many industrial and consumer applications of clay minerals, and nanotubular halloysite (HNT) has been used extensively for such purposes; performance enhancements are still needed, however. The objective of the present study was to improve the gas-adsorption capacity of HNT by controlling the particle size and porosity. This was accomplished through acid treatment and particle-size fractionation by centrifugation. Various particle sizes were obtained and porosities ranged from macropores to mesopores. Natural halloysite nanotubes were modified by sulfuric acid in various concentrations to selectively remove the alumina composition of the tubes. X-ray diffraction and energy dispersive X-ray spectroscopy were used to verify the mineralogical and compositional changes. Surface modification by the acid treatment increased the inner space volume of the tubes and decreased the mass of the nanotubes because of the elimination of alumina. The gas adsorption capacity of both natural and modified halloysite nanotubes was measured quantitatively using N2 adsorption and the Brunauer-Emmett-Teller (BET) method, and the morphology was determined from transmission electron microscopy (TEM) images. The results showed that the modified halloysite nanotube was 7.47 times more efficient at gas adsorption than pristine halloysite. Moreover, the dealumination of the surface increased the inner space. Greatly increased porosity characteristics, including gas adsorption and macroporosity, were obtained through modification by acid treatment.

Experimental illitization of smectite was studied by transmission electron microscopy (TEM) and X-ray diffraction (XRD). Experiments were performed on the <2 µm fraction consisting entirely of smectite separated from a soil formed on subvolcanic rock located in the External Zone of the Betic Cordilleras (southern Spain). Amounts of 0.25 g were added to different solutions: seawater, and three K-enriched seawater solutions prepared by adding KOH to seawater whose final [K] values were 0.1, 0.5 and 1 M, respectively. The experiments were performed at 50°C over a period of 30 days. The XRD patterns showed no mineralogical changes in residues from seawater or from the 0.1 M [K] solution. With increasing pH and K molarity, the smectite peak, initially at 1.4 nm, became broader. This change in the smectite peak was more significant in the residue from the 1 M [K] solution. The appearance of a small shoulder at 1.0 nm in the residue from a 0.5 M [K] solution showed the beginning of illite formation. However, its appearance was clearer in XRD patterns of the residue corresponding to the 1 M [K] solution. The XRD data from air-dried, glycolated, and heated samples from the 1 M [K] solution indicated the presence of smectite, disordered interstratified illite-smectite (I-S) and illite.

The TEM/AEM studies were performed on the residue corresponding to the 1 M [K] experiment. The HRTEM images revealed that smectite and illite occurred as separated packets with a ferroan lizardite, as a by-product of the smectite-to-illite reaction, interstratified and intergrown with illite. Smectite occurs both as ‘rims’ on the illite packet and in its core. The presence of smectite in the core of illite packet indicates that the lateral transition from smectite to illite was incomplete, taking place by direct replacement of smectite layers as a whole through a dissolution-precipitation mechanism. The experimental study shows that smectite may transform in a wide range of geological and artificial environments involving high-pH K-rich solutions.